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Relative Permittivity As A Function Of Co-Solvent And Impedance Spectroscopy For Quantifying Anions In Solution, Yahya Sami Alseiha 2018 East Tennessee State University

Relative Permittivity As A Function Of Co-Solvent And Impedance Spectroscopy For Quantifying Anions In Solution, Yahya Sami Alseiha

Electronic Theses and Dissertations

This work measured relative permittivity from 15.0 to 55.0 °C of aqueous solutions containing acetone or tetrahydrofuran using a BI 870 dielectric meter. A cubic polynomial fit resulted in coefficients for calculating permittivity as a function of temperature and mole fraction. Literature values for other co-solvent system resulted in similar polynomial coefficients. Using BI 870, permittivity measurements of ionic solutions were not possible because of high conductivity. A simple method using impedance spectroscopy measured these solutions. Impedance decreases with increasing temperature and decreases with increasing ionic strength. Due to the temperature dependence of impedance, all measurements were at ...


34 - Using Atomic Force Microscopy To Image Metal Sulfide Nanoparticles, Martin Driggers, Tatiana Mendoza, George Chumanov 2018 Clemson University

34 - Using Atomic Force Microscopy To Image Metal Sulfide Nanoparticles, Martin Driggers, Tatiana Mendoza, George Chumanov

Georgia Undergraduate Research Conference (GURC)

Using Atomic Force Microscopy to Image Metal Sulfide Nanoparticles

Martin Driggers, Tatiana Estrada-Mendoza, and Professor George Chumanov

Department of Chemistry, Clemson University

This research project is focused on the use of Atomic Force Microscopy (AFM) to image metal sulfide nanoparticles. The nanoparticles were synthesized in a solution by reacting metal salts with sodium sulfide in the presence of a silica matrix and have the potential for many applications including electronics, photovoltaics, and biomedical diagnostic. With the right concentrations of sulfur, silica, and metal ions, non-aggregated metal sulfide nanoparticles can be synthesized in an aqueous solution, stabilized by silica. The size ...


The Electrochemical Study Of Simulated Spent Nuclear Fuel (Simfuel) Corrosion Under Permanent Disposal Conditions, Ziyan Zhu 2018 The University of Western Ontario

The Electrochemical Study Of Simulated Spent Nuclear Fuel (Simfuel) Corrosion Under Permanent Disposal Conditions, Ziyan Zhu

Electronic Thesis and Dissertation Repository

The safety assessment of spent nuclear fuel under permanent disposal conditions requires examination of the corrosion of the spent fuel waste form (UO2) inside a failed waste container. The objective of this research project was to develop a detailed mechanism of the UO2 corrosion process when exposed to groundwater. The redox conditions within a failed container in a deep geologic repository will be complex. The oxidant, H2O2, produced by the α-radiolysis of groundwater, will be the main driving force for fuel corrosion. However, the efficiency of fuel dissolution will be determined by the competition between ...


‘Cassette’-Ises (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds For Hydrolytic Kinetic Resolution Across A Range Of Epoxides, Sangeeta Dey, Douglas R. Powell, Chunhua Hu, David B. Berkowitz 2018 University of Nebraska - Lincoln

‘Cassette’-Ises (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds For Hydrolytic Kinetic Resolution Across A Range Of Epoxides, Sangeeta Dey, Douglas R. Powell, Chunhua Hu, David B. Berkowitz

Faculty Publications -- Chemistry Department

‘Cassette’-ISES (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds for Hydrolytic Kinetic Resolution Across a Range of Epoxides

A new ‘Cassette’-In Situ Enzymatic Screen (ISES) for combinatorial catalysis is introduced. This allows the experimentalist to obtain an information-rich readout, in real time, providing an estimate of the sense and magnitude of enantioselectivity across more than one substrate. In its first iteration, the screen identified CoIII-salen catalysts with β-pinene- and α-naphthylalanine-derived chiral scaffolds with broad, yet complementary, substrate specificities.


Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman 2018 University of Kentucky

Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman

Chemistry Faculty Publications

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic ...


Nanoparticle Microarray For High-Throughput Microbiome Metabolomics Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry, Rebecca L. Hansen, Maria Emilia Duenas, Torey Looft, Young Jin Lee 2018 Iowa State University

Nanoparticle Microarray For High-Throughput Microbiome Metabolomics Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry, Rebecca L. Hansen, Maria Emilia Duenas, Torey Looft, Young Jin Lee

Chemistry Publications

A high-throughput matrix-assisted laser desorption/ionization mass spectrometry (MALDI)-MS-based metabolomics platform was developed using a pre-fabricated microarray of nanoparticles and organic matrices. Selected organic matrices, inorganic nanoparticle (NP) suspensions, and sputter coated metal NPs, as well as various additives, were tested for metabolomics analysis of the turkey gut microbiome. Four NPs and one organic matrix were selected as the optimal matrix set: α-cyano-4-hydroycinnamic acid, Fe3O4 and Au NPs in positive ion mode with 10 mM sodium acetate, and Cu and Ag NPs in negative ion mode with no additive. Using this set of five matrices, over two thousand unique ...


Developing A New Sensing Technology For Double-Stranded Dna Detection Utilizing Engineered Zinc Finger Proteins And Nanomaterials, Dat Thinh Ha 2018 Western Kentucky University

Developing A New Sensing Technology For Double-Stranded Dna Detection Utilizing Engineered Zinc Finger Proteins And Nanomaterials, Dat Thinh Ha

Masters Theses & Specialist Projects

A specific double-stranded DNA sensing system is of great interest for diagnostic and other biomedical applications. Zinc finger domains, which recognize double-stranded DNA, can be engineered to form custom DNA-binding proteins for recognition of specific DNA sequences. As a proof of concept, a sequence-enabled reassembly of TEM-1 β- lactamase system (SEER-LAC) was previously demonstrated to develop zinc finger protein (ZFP) arrays for the detection of a double-stranded bacterial DNA sequence. Here, we implemented the SEER-LAC system to demonstrate the direct detection of pathogenspecific DNA sequences present in E. coli O157:H7 on the lab-on-a chip. ZFPs customdesigned to detect shiga ...


Hydrogen-Deuterium Exchange Mass Spectrometry And Molecular Dynamics Simulations For Studying Protein Structure And Dynamics, Yiming Xiao 2018 The University of Western Ontario

Hydrogen-Deuterium Exchange Mass Spectrometry And Molecular Dynamics Simulations For Studying Protein Structure And Dynamics, Yiming Xiao

Electronic Thesis and Dissertation Repository

Deciphering properties of proteins are essential for human health and aiding in the development of new pharmaceuticals. This dissertation uses hydrogen-deuterium exchange (HDX) mass spectrometry (MS) and molecular dynamics (MD) simulations to study protein dynamics, for improving the understanding of protein folding/unfolding mechanisms, and ligand binding and allosteric regulation.

Chapter 2 uses HDX-MS for probing the conformational dynamics of myoglobin in the presence of N2 bubbles. We propose a dynamic model that reproduces the observed data: “semi-unfolded” “native” “globally unfolded” -> “aggregated”. Chapter 3 focuses on osteoprotegerin (OPG), which hinders bone resorption by inhibiting RANK/RANKL interactions. The dimerization ...


Mechanism Of Protein Charging And Supercharging In Electrospray Ionization: Molecular Dynamics Simulations And Experimental Investigations, Haidy S. Metwally 2018 The University of Western Ontario

Mechanism Of Protein Charging And Supercharging In Electrospray Ionization: Molecular Dynamics Simulations And Experimental Investigations, Haidy S. Metwally

Electronic Thesis and Dissertation Repository

Electrospray ionization mass spectrometry (ESI-MS) is a powerful technique for investigating protein structures, conformations, and interactions. Despite its widespread use, many fundamental aspects of ESI remain poorly understood. In this thesis, we use a combination of molecular dynamics (MD) simulations and experiments to gain insights into the hidden complexities of ESI-MS.

Chapter 2 discusses the topic of salt-induced protein signal degradation. Salts such as NaCl, CsCl, and tetrabutyl ammonium chloride (NBu4Cl) interfere with MS data acquisition, leading to adduct formation and signal suppression. MD simulations provide an explanation for these salt interferences. Signal suppression can be broken down ...


An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman 2018 University of Kentucky

An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman

Chemistry Faculty Publications

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric ...


Characterization And Quantification Of Covalent Modification Of Proteins Using Mass Spectrometry, Pratikkumar N. Rathod 2018 The Graduate Center, City University of New York

Characterization And Quantification Of Covalent Modification Of Proteins Using Mass Spectrometry, Pratikkumar N. Rathod

All Dissertations, Theses, and Capstone Projects

Identification and characterization of various post-translational modifications of protein is a key to understanding many unknown cellular processes. In the last few decades, mass spectrometry has evolved as an essential and effective analytical tool for qualitative and quantitative analysis of proteins. In this research, we have developed a novel MALDI-MS2 based quantification method for Desmosine and Isodesmosine, which served as cross-linking amino acids of elastin, in order to measure the elastin degradation in the body. This is the first quantification method that not only illustrates the potential of MALDI-Ion Trap MS2, but also improvement over the current LC-MS ...


Determination Of Polar Solvents By Static Headspace Extraction – Gas Chromatography (She-Gc), Michael Sithersingh 2018 Seton Hall University

Determination Of Polar Solvents By Static Headspace Extraction – Gas Chromatography (She-Gc), Michael Sithersingh

Seton Hall University Dissertations and Theses (ETDs)

ABSTRACT

The term “headspace” is defined as the vapor that forms above or around a liquid or solid sample in a closed container. Usually, the vapor is above the liquid or solid at the top of the container, hence the term headspace. Headspace sampling is a method for separating volatile materials that may be extracted from a more solid sample matrix and then analyzed using gas chromatography. Headspace extraction refers to the collection and analysis of the vapor phase in the container. The Static Headspace Extraction – Gas Chromatography (SHE-GC) technique has been used since the early days of Gas Chromatography ...


Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman 2018 University of Kentucky

Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman

Chemistry Faculty Publications

Understanding the acid–base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants ...


Immobilization Of Gold Nanoparticles On Nitrided Carbon Fiber Ultramicroelectrodes By Direct Reduction, George Affadu-Danful 2018 East Tennessee State University

Immobilization Of Gold Nanoparticles On Nitrided Carbon Fiber Ultramicroelectrodes By Direct Reduction, George Affadu-Danful

Electronic Theses and Dissertations

Due to enhanced properties such as large surface area-to-volume ratio, metal nanoparticles are often employed as catalysts for various applications. However, most studies involving nanoparticle catalysts have been conducted on collections of particles rather than single nanoparticles. Results obtained for ensemble systems can be difficult to interpret due to variations in particle loading and interparticle distance, which are often challenging to control and characterize. In this study, two immobilization strategies for incorporating gold nanoparticles (AuNPs) on carbon fiber ultramicroelectrodes (UMEs) were compared with the goal of extending these techniques to nanoelectrodes for studies of single AuNPs. Both layer-by-layer deposition of ...


Comparing Laser Assisted Pulling And Chemical Vapor Deposition Methods In The Fabrication Of Carbon Ultramicro- And Nanoelectrodes, Theophilus Neequaye 2018 East Tennessee State University

Comparing Laser Assisted Pulling And Chemical Vapor Deposition Methods In The Fabrication Of Carbon Ultramicro- And Nanoelectrodes, Theophilus Neequaye

Electronic Theses and Dissertations

Ultramicroelectrodes (UMEs) (limiting dimensions <~25 μm) and nanoelectrodes (<~100 nm) exhibit enhanced electrochemical properties compared to macroscopic electrodes. Their small sizes and enhanced properties make them well-suited for various interesting and important applications such as measuring redox-active species in nonaqueous solvents, studying intermediates of fast electrochemical reactions, and investigating electrochemical and electrocatalytic properties of single nanoparticles. While UMEs are commercially available, nanoelectrode fabrication is still largely confined to research labs. Various methods for constructing nanoelectrodes have been reported and continue to be developed, but most require considerable expertise, and comparisons between different fabrication processes are lacking. In this work, a comparison of laser-assisted pulling and chemical vapor deposition (CVD) methods of electrode fabrication is made with the aim of optimizing production of carbon nanoelectrodes for single nanoparticle electrochemical measurements. By examining effects of pulling parameters, post-pulling treatments, and CVD processing, electrodes as small as ~50 nm were successfully produced.


Hydrolysis Of Cellulose And Biomass Using Blue Molybdenum, Farouk Awudu 2018 East Tennessee State University

Hydrolysis Of Cellulose And Biomass Using Blue Molybdenum, Farouk Awudu

Electronic Theses and Dissertations

Hydrolysis of cellulosic biomass is an important and ongoing subject of research due to generating precursors for biofuel synthesis. This work involves hydrolysis of microcrystalline cellulose and Arundo donax to glucose. Methods for acid hydrolysis include the use of sulfuric acid, phosphomolybdic acid, blue molybdenum using low concentrations at 40-100 °C. For comparison purposes, enzymatic hydrolysis was also carried out using cellulase. Products were quantified by measuring total organic carbon and reducible sugars using dinitrosalicylic acid. Use of phosphomolybdic acid, blue molybdenum and sulfuric acid even at 6.0 M did not increase the amount of glucose compared to using ...


3d-Printed Fluidic Devices And Incorporated Graphite Electrodes For Electrochemical Immunoassay Of Biomarker Proteins, Abdulhameed Alabdulwaheed 2018 East Tennessee State University

3d-Printed Fluidic Devices And Incorporated Graphite Electrodes For Electrochemical Immunoassay Of Biomarker Proteins, Abdulhameed Alabdulwaheed

Electronic Theses and Dissertations

Biomarkers are measurable indicators of health status or disease state that can be used for diagnosis and may help guide patient treatment strategies. Enzyme-linked immunosorbent assays (ELISA) and other many clinical techniques currently used for measuring biomarker proteins lack sensitivity, demand high analysis cost, are often not well-suited for measuring multiple biomarkers in a single sample, and require long analysis times. Here, we demonstrate simple, low-cost 3D-printed flow-through devices with integrated electrodes modified with gold nanoparticles (AuNPs) for electrochemical immunoassays of S100B, a biomarker protein related to conditions like skin cancer and brain injuries. Flow-through devices are fabricated from photocurable-resin ...


Manganese Oxide/Hemin-Functionalized Graphene As A Platform For Peroxynitrite Sensing, Haitham F. Kalil, Shaimaa Maher, Tiyash Bose, Mekki Bayachou 2018 Cleveland State University

Manganese Oxide/Hemin-Functionalized Graphene As A Platform For Peroxynitrite Sensing, Haitham F. Kalil, Shaimaa Maher, Tiyash Bose, Mekki Bayachou

Chemistry Faculty Publications

Peroxynitrite (ONOO−, PON) is a powerful oxidizing agent generated in vivo by the diffusion-limited reaction of nitric oxide (NO) and superoxide (O2˙) radicals. Under oxidative stress, cumulated peroxynitrite levels are associated with chronic inflammatory disorders and other pathophysiological conditions. The accurate detection of peroxynitrite in biological systems is important, not only to understand the genesis and development of diseases, but also to explore and design potential therapeutics. Herein, a manganese oxide/hemin-modified graphene interface is explored as a platform for peroxynitrite amperometric detection. Hemin-functionalized reduced graphene oxide was further modified with manganese oxide nanoparticles to provide a composite material ...


Novel Relative Spontaneous Ignition Temperature Determination Using Carbon Dioxide Onset With Sta/Ir, Antonio David Trevino 2018 Stephen F. Austin State University

Novel Relative Spontaneous Ignition Temperature Determination Using Carbon Dioxide Onset With Sta/Ir, Antonio David Trevino

Electronic Theses and Dissertations

Simultaneous thermal analysis, coupled with infrared spectroscopy (STA/IR), was utilized to monitor the evolution of gaseous products during the thermal degradation of samples from Triadica sebifera (Chinese tallow), Ligustrum sinense (Chinese privet), and Ilex vomitoria (yaupon) plants. Identification of carbon dioxide was successful with a spectral match of 90.2 percent and further used in the determination of relative spontaneous ignition temperature, or RSIT. The RSIT value during the growing season for Chinese tallow, Chinese tallow stem, Chinese privet, and Yaupon were 208.4°C, 250.3°C, 210.1°C, and 232.3°C respectively. During the dormant ...


Bayesian Analytical Approaches For Metabolomics : A Novel Method For Molecular Structure-Informed Metabolite Interaction Modeling, A Novel Diagnostic Model For Differentiating Myocardial Infarction Type, And Approaches For Compound Identification Given Mass Spectrometry Data., Patrick J. Trainor 2018 University of Louisville

Bayesian Analytical Approaches For Metabolomics : A Novel Method For Molecular Structure-Informed Metabolite Interaction Modeling, A Novel Diagnostic Model For Differentiating Myocardial Infarction Type, And Approaches For Compound Identification Given Mass Spectrometry Data., Patrick J. Trainor

Electronic Theses and Dissertations

Metabolomics, the study of small molecules in biological systems, has enjoyed great success in enabling researchers to examine disease-associated metabolic dysregulation and has been utilized for the discovery biomarkers of disease and phenotypic states. In spite of recent technological advances in the analytical platforms utilized in metabolomics and the proliferation of tools for the analysis of metabolomics data, significant challenges in metabolomics data analyses remain. In this dissertation, we present three of these challenges and Bayesian methodological solutions for each. In the first part we develop a new methodology to serve a basis for making higher order inferences in metabolomics ...


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