Physical Sciences and Mathematics Commons^™

Design, Synthesis, And Characterization Of Complex Chalcogenides For Energy Storage And Energy Conversion Applications, Srikanth Balijapelly

Doctoral Dissertations

"Through this investigation, complex chalcogenides with the combination of main group metals, transition metals, and rare earth metals have been synthesized using the building block approach and their structure-property relationships are evaluated. The main emphasis of research is on rationally designing new materials for applications in sodium and lithium ion conducting solid electrolytes, cathodes, thermoelectrics, and nonlinear optics. Along with the experimental studies, theoretical calculations are also employed to better understand the physicochemical properties of the synthesized compounds.

The first part of the research will discuss designing alkali ion containing complex chalcogenides using the building block approach. This investigation resulted …

Chirality Determination Using Three-Wave Mixing Microwave Spectroscopy, Nicole Taylor Moon

Doctoral Dissertations

"Rotational spectroscopy has established itself as a reliable gas-phase spectroscopic technique for the structural determination of molecules. This reliability has stemmed from both advancements in microwave technology and a willingness from the community to push the boundaries of the field. In this dissertation, the boundaries are tested in both how well the technique can determine the structure of molecules exhibiting large amplitude motion and through chirality determination. The first half of this dissertation explores the use of deep averaging to determine the structure of silicon containing molecules in collaboration with Dr. Guirgis from the College of Charleston. For each of …

Electrodeposition Of Epitaxial Wide Bandgap P-Type Semiconductors And Copper Metal For Energy Conversion And Flexible Electronics, Bin Luo

Doctoral Dissertations

"Epitaxial electrodeposition is a simple, low-cost technology to produce highly ordered materials on single-crystal surfaces. This research focuses on the epitaxial electrodeposition of wide bandgap p-type semiconductors and epitaxial Cu thin films via a self-assembled monolayer for energy conversion and flexible electronics. Paper I introduces the epitaxial electrodeposition of hole conducting CuSCN nanorods onto Au (111) surface, and lift-off to produce flexible and transparent foils. Highly ordered CuSCN could serve as an inorganic transport layer in various opto-electronic devices such as perovskite solar cells, LEDs, and transistors. An ordered and transparent CuSCN foil was also produced by epitaxial lift-off following …

Fluorination Of Rubisco-Mimetic Co2 Capture Systems. Theoretical And Experimental Studies Of Ammonium Ion Acidity Depression And Carbamylation, Brian Michael Jameson

Doctoral Dissertations

"RuBisCO-inspired CO₂ capture and release (CCR) systems featuring amines have been developed for the purpose of reversable CO₂ capture from air. The enzyme active site consists of the tetrapeptide sequence Lys-Asp-Asp-Glu. The Lys sidechain amine undergoes carbamylation and an Mg²⁺ cation stabilizes the resulting carbamate. The N^a-acyl-lysinyl-aspratyl-aspartyl-glutamide (Lys-Asp-Asp-Glu, KDDE) peptide featured maximum capture at pH ≈ 10; a pH region too high for Mg²⁺ ions to remain in solution. This work aims to achieve pKa depression by introducing fluorine in the proximity of the lysine’s sidechain amine. A comparative analysis was made of butylamine, …

Design And Synthesis Of Purine Based Neuroprotectors And Novel Synthetic Methods For The Trifluoromethylation Of Aldehyde Hydrazones, Puspa Aryal

Doctoral Dissertations

"Purine-derived compounds are widely investigated as cyclin-dependent kinase inhibitors that have broad applications in the design of pharmaceuticals for treating diseases, such as diabetes, atherosclerosis, and cancers. Towards the goal of effective AGE-inhibitors, and neuroprotector compounds we have synthesized a series of novel purine-based triazoles and investigated their neuroprotective effects, using SHSY-3Y human neuroblastoma cell line. Through these studies, we have identified purine-based neuroprotector compounds that favorably modulate oxidative stress induced by the Fenton reaction-generated reactive oxygen species (ROS).

The C(sp²−H)-trifluoromethylation of hydrazones would give access to the αtrifluoromethylated hydrazones that can serve as intermediates in the synthesis …

Synthesis, Characterization And Chemistry Of Two-Dimensional Transition Metal Carbides And Nitrides (Mxenes), Shuohan Huang

Doctoral Dissertations

"MXenes represent a relatively new and quickly growing family of two-dimensional (2D) early transition-metal carbides and nitrides first synthesized in 2011 from bulk layered crystalline MAX phases. Because of their 2D structure and unique combination of high conductivity and hydrophilicity, MXenes have raised a significant interest for various applications. However, it has been found that in some cases colloidal MXene flakes are not stable and can spontaneously degrade on a time scale from hours to days. In this work, we investigate the crucial factors for MXene degradation and demonstrate gas analysis as a powerful method to gain further insights into …

Synthesis And Process Optimization Of Colloidal Unimolecular Polymer, Cup, Particle Formation, And Its Interfacial Surface Tension Behavior, Ashish Zore

Doctoral Dissertations

"Colloidal Unimolecular Polymer (CUP) particles are 3-9 nm size single-chain polymer nanoparticles that are made from amphiphilic acrylic co-polymers using the process of water reduction. The formation of CUP particles was driven by the polymer-polymer interactions being greater than polymer-solvent interactions as well as the charge-charge repulsion due to the increasing dielectric of the medium. CUPs provide a surfactant or additive-free nanoparticle system that was useful for studying the interfacial behavior of pure aqueous nanoparticles using a maximum bubble pressure tensiometer. The equilibrium surface tension shows a dependence on concentration and the charge density of the CUP particle. The equilibrium …

Establishing Pteridine Metabolism In A Breast Cancer Cell Model And Quantification Of Silver Nanoparticle Interactions With Yeast Cells Using Mass Spectrometry, Lindsey Katherine Rasmussen

Doctoral Dissertations

"Recent advances in analytical methods have furthered the quantitative insights that can be gleaned from cellular analyses, with applications in cancer and nanoparticle research. In the first part of the research presented, a recently developed HPLC-MS/MS method was advanced to elucidate pteridine metabolism in an isogenic progressive MCF10A breast cancer cell model. The folate-derived pteridine pathway in breast cells was established by individually dosing cell cultures with folic acid and 15 pteridines. Eight potential pteridine biomarkers in breast cancer cells were identified including pterin and isoxanthopterin, which yielded the first in vitro evidence for the cellular metabolisms behind previously reported …

Electrocatalytic Processes For Energy Storage & Conversion, Apurv Saxena

Doctoral Dissertations

"The continuous excessive usage of fossil fuels has resulted in its fast depletion leading to an escalating energy crisis as well as several environmental issues leading to increased research towards sustainable energy conversion. Electrocatalysts play crucial role in the development of numerous novel energy conversion devices including fuel cells and solar fuel generators.

High-efficiency and cost-effective catalysts are required for large-scale implementation of these new devices. Over the last few years transition metal chalcogenides have emerged as highly efficient electrocatalysts for several electrochemical devices such as water splitting, carbon dioxide electroreduction and, solar energy converters. These transition metal chalcogenides exhibit …

Fabrication, Characterization And Environmental Monitoring Of Polymer-Based Materials For Biomedical And Structural Applications, Mousumi Bose

Doctoral Dissertations

"Polymers are versatile materials utilized for variety of applications. In biomedical field, luminescence quenching based optical oxygen sensors encapsulated in polymeric substances are gaining attention for early detection of surface wounds associated with tissue oxygen. A simple and low-cost fabrication technique was developed to produce sensor arrays for continuous two-dimensional oxygen tension measurement. Sensor patch along with smart phone-based readout technique is being evaluated as a smart bandage.

The environmental concerns and limited petroleum supply demand for replacing petroleum-based polymers with renewable bio-based sources while maintaining comparable properties. A sustainable and green approach was adopted to synthesize soy polyol-derived rigid …

Novel Synthetic Methods And Applications Of Porous Materials: Aerogel Foams, Metallic Aerogels, Amorphous And Graphitic Carbon Aerogels, Rushi Soni

Doctoral Dissertations

"We report novel methods for the synthesis of porous materials such as polymeric aerogel foams, pure metallic aerogels, amorphous and graphitic carbon aerogels, and their applications. I. Polyurethane based aerogel foams were synthesized with an aliphatic triisocyanate and ethylene glycol through a pressurized (7 bar) sol-gel method. The foam-like structure is prepared without any chemical foaming agents or templates, resulting in less expensive, more efficient, readily adaptable, and environmentally friendly process. Those materials exhibited lower thermal conductivity (by 25%) and higher oil adsorption capacity (by 36% w/w) than their corresponding aerogels. II. Monolithic, pure metallic Co(0) aerogels were synthesized from …

High Throughput Analysis To Study Emerging Pollutants And Nanoparticle Fate In Biological Systems, Xiaolong He

Doctoral Dissertations

”The increasing applications of emerging and fugitive contaminants (EFCs) and engineered nanoparticles (ENPs) attract significant research interest for their potential risks to human health and the environment. In order to assess the health risks of these emerging contaminants, rapid and reliable analytical methods to measure the concentrations and fates of these contaminants are imperative. This dissertation focuses on the developments of advanced analytical methods and their applications to study those emerging contaminants in crop plant and simulated gastric fluid (SGF). Three types of mass spectrometry based methodologies have been developed, one is freeze-thaw/centrifugation extraction followed by high performance liquid chromatography …

Development Of Intelligent Stimuli-Responsive Biomaterials And Nanodevices, Shuo Yang

Doctoral Dissertations

"Structural DNA nanotechnology utilizes DNA molecules as building blocks to fabricate ordered artificial nanostructures at the molecular level. Among all DNA-based techniques, DNA origami has been considered as one of the most powerful tools for constructing artificial nanostructures with excellent programmability and addressability. Currently, most DNA origami nanostructures are static and do not have the ability to response to environmental stimulation. The development of environmental-responsive DNA origami nanostructures is a critical step towards the realization of intelligent dynamic DNA origami-based nanodevices. This research focuses on the design and fabrication process of both static and dynamic DNA origami nanostructures and their …

Development Of Tripodal And Bipodal Ligand Frameworks And First-Row Transition Metal Reagents For Selective C-N Bond Construction Methodologies, Anshika Kalra

Doctoral Dissertations

"We present a family of anionic Mn(II) reagents supported by trisphenylamido- amlne frameworks that offer guidance with regards to ligand selection for developing C—N bond construction methodologies (extensively used in the synthesis of petrochemicals, household chemicals) through nitrene- transfer chemistry. We subsequently extend the study to include the corresponding Fe(II), Co(II), and Ni(II) reagents, to gain insights in their comparative reactivity/selectivity patterns. Attenuated levels of electrophilicity of anionic complexes proved to be more suitable for discriminating aromatic from aliphatic olefins for aziridination purposes, especially for Mn(II) complexes. However, in the case of Co(II) reagents, we observe that additional stereoelectronic parameters …

Relating Detonation Parameters To The Detonation Synthesis Of Nanomaterials, Martin Langenderfer

Doctoral Dissertations

“This research investigates the physical and chemical processes that contribute to the detonation synthesis of silicon carbide nanoparticles. Bulk production of SiC nanoparticles through detonation is possible due to pressures achieved over 20 GPa and temperatures over 2000 K as well as quenching rates in excess of 13 billion K/second. These conditions catalyze reaction and bottom-up molecular growth while retaining particles < 100 nm in diameter. In this work, detonation synthesis of SiC was demonstrated by incorporation of polycarbosilane, an SiC precursor material, into an RDX/TNT explosive matrix prior to detonation. Detonation Synthesis of SiC was also accomplished by reacting elemental silicon with carbon liberated by the detonation of negatively oxygen balanced TNT. Hydrodynamic simulation of a 60:40 mass ratio RDX/TNT detonation created conditions thermodynamically suitable to produce cubic silicon carbide within the first 500 nanoseconds after the passage of the detonation wave while carbon remains chemically reactive for molecular formation. Simulations and experimental tests indicated that loading configuration and impedance mismatch of the precursor additives used in detonation synthesis results in conditions in the additives that exceed the accepted detonation pressure of the explosive by greater than three times. Finally, a full factorial experimental design showed increasing silicon concentration, reducing silicon size, and reducing oxygen balance by adjusting the ratio of RDX to TNT decreased the explosives detonation pressure by 20% and increased the soot yield and concentration of SiC observed in the detonation products by 82% and 442% respectively”--Abstract, page iv.

Development Of High-Performance Hydrogels, Buddhabhushan Salunkhe

Doctoral Dissertations

Here, we present a systematic approach to design robust hydrogel compositions. The goal was to achieve excellent properties to open up new opportunities in especially two challenging applications not previously well-served by hydrogels.

The first part of this research will discuss the systematic screening of polymers for their hydrothermal stability under brine, acidic, neutral, and basic pH conditions followed by novel designs of hydrogel compositions. Certain hydrogel compositions withstand temperatures of up to 150 °C for more than 24 months in high salinity brines. This novel hydrogel composition fills a technology gap between the existing polyacrylamide-based preformed particle gels (PPGs) …

Designing Transition Metal Chalcogenides Electrocatalyst Surfaces For High-Efficiency Water Oxidation, Umanga De Silva

Doctoral Dissertations

”The rising demand for energy security and reducing fossil fuel dependence has prompted researchers to search for a clean, sustainable, and efficient energy generation system with low environmental impact. Water electrolysis has been identified as one of the most important processes satisfying the above needs to generate hydrogen as a clean fuel. Two half-cell reactions of oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode comprise the main process of water electrolysis. However, the oxygen evolution reaction is the most crucial step for efficient water splitting. Traditionally, metal oxides have been utilized as catalysts …

Continuous-Flow Synthesis Of Fine Chemicals And Pharmaceutical Compounds Over Intelligent Organocatalysts With Bifunctional Reactivity, Abdo-Alslam Alwakwak

Doctoral Dissertations

“Many biological systems that utilize organic active sites to catalyze reactions under mild conditions invoke cooperative catalytic pathways, whereby two or more active sites work together to activate the reactant(s). The use of cooperative (bifunctional) catalysts and continuous flow chemistry (a reaction within the narrow channels of a micro‐ or microfluidic reactor) are commonplace in sustainable chemical transformation and attract a great deal of interest with respect to economic and environmentally-sustainable production of fine chemicals, pharmaceuticals, and agrochemicals, water treatment, as well as upgrading of biomass feedstocks. Although, some methods have been developed for immobilization of bifunctional catalysts for cooperative …

Tools To Evaluate Nanodiamond-Mediated Delivery Of Tiopronin For Cataract Prevention, Justin Beltz

Doctoral Dissertations

”There is a growing demand for non-surgical means of cataract treatment. This dissertation presents three bodies of work that reflect the early-stage development of eye drop formulations aimed at delaying cataract progression. These formulations consist of the antioxidant 2-mercaptopropionylglycine (MPG) loaded onto nanodiamond particles.

Cataractogenesis is linked to oxidative damage to lens proteins. To investigate the potential of MPG for protection against oxidative damage, A549 cells were incubated in 0.6 mM tert-butylhydroperoxide (tBHP). Cells exposed to tBHP without MPG exhibited elevated levels of reactive oxygen species, which led to the depletion of the vital antioxidant glutathione and, ultimately, apoptosis. Co-administration …

Synthesis And Thermodynamic Characterization Of Free And Surface Water Of Colloidal Unimolecular Polymer (Cup) Particles Utilizing Dsc And Tga, Peng Geng

Doctoral Dissertations

“Colloidal Unimolecular Polymer (CUP) is spheroidal nanoscale polymer particle (3-9 nm) with charged hydrophilic gruops on the surface and a hydrophobic core. The formation of CUPs involves a simple free radical polymerization and a water reduction process. CUPs are thermodynamically stable in water, molecular weight, particle size and charge density can be designed and controlled. CUPs have a layer of surface associated water, due to the small particle size, the surface water/CUP volume ratio is ultra-high. Therefore, CUP is a very promising candidate to investigate the thermodynamic of surface water characteristics. In addition, CUP solution is free of surfactant and …

Structurally And Electronically Diverse Polyanion-Based Cathode Materials For Alkali-Ion Batteries, Prashanth Sandineni

Doctoral Dissertations

”Through this investigation polyanion-based cathode materials including sulfates, phosphates, and phosphites of transition metal have been synthesized for lithium and sodium-ion batteries and their electrochemical performances were evaluated. The emphasis was on soft chemical routes to discover metastable phases which are often missed in high temperature synthesis. Iron-based compounds were the main focus of this investigation, however, concurrently a few vanadium-analogues of iron compounds were investigated to evaluate the effect of multi-electron process on achievable voltage and capacity.

This investigation resulted in the discovery of several compounds with unique crystal structures, namely AFe₃(SO₄)₂(OH)_{6 …}

Transition Metal Chalcogenide Hybrid Systems As Catalysts For Energy Conversion And Biosensing, Siddesh Umapathi

Doctoral Dissertations

"Generation of hydrogen and oxygen through catalyst-aided water splitting which has immense applications in metal air batteries, PEM fuel cells and solar to fuel energy production, has been one of the critical topics in recent times. The state of art oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) catalysts are mostly comprised of precious metals. The current challenge lies in replacing these precious metal-based catalysts with non-precious earth-abundant materials without compromising catalytic efficiency.

This research explores mixed metal selenides containing Fe-Ni, Fe-Co and RhSe which were hydrothermally synthesized and/or electrodeposited and tested for OER and ORR …

Stabilization Dynamics Of The Ozone Molecular System, Sangeeta Sur

Doctoral Dissertations

"The observation of larger-than-expected concentrations of heavier isotopologues of ozone known as 'ozone isotopic anomaly' in the stratosphere is a mass-independent effect (in contrast to most kinetic isotope effects familiar to chemists) that is traced back to the recombination process in the formation of ozone in the Chapman cycle. Understanding the relative efficiencies (often approximated as equal for different isotopologues) of the stabilization step (some of the details of which are still a mystery) which involves energy transfer from a highly excited ozone molecule to a third body, M (argon atom in this case) to form stable ozone is a …

Nanodiamonds And Carbon Nano-Onions Ceramic Composites And Their Applications, Ibrahim Munkaila Abdullahi

Masters Theses

"Luminescent nanodiamonds are photostable non-blinking fluorescent biocompatible, non-toxic, functional Zable materials made from high-pressure high temperature (HPHT) microcrystalline diamonds. For long, the scientific community has been investigating for a clean, efficient and cost-effective technique to reduce the size of fluorescent microcrystalline diamond into nanodiamonds. Their color center, responsible for the fluorescent properties are crucial for their applications, including biomedical imaging, nano sensing, quantum computing etc, and therefore should not be affected significantly by the method of size reduction applied. A novel size reduction technique that is based on explosive fragmentation was developed and the corresponding fragmented diamonds obtained were characterized …

Mass Spectrometry Analysis Of Contaminants Of Emerging Concern: Nanoparticles, Algal Toxins, And Cyanotoxins In Natural Waters And Their Potential Health Impacts, Ariel R. Donovan

Doctoral Dissertations

“The analysis of contaminants of emerging concern is critical to protecting environmental health. In the presented dissertation, two groups of contaminants of emerging concern were assessed using mass spectrometry methods: nanoparticles and algal and cyanotoxins.

Analysis of metal oxide nanoparticles in environmental matrices has been a challenging issue, as most traditional methods require complicated sample preparation methods or that can alter or destroy the nanoparticles in the system. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) methods were used to detect metal oxide nanoparticles in surface waters and their removal through drinking water treatment simulations while retaining all information regarding …

Design, Synthesis, Characterization And Anti-Cancer Effects Evaluation Of Interchain Cysteine Linked Antibody Drug Conjugates, Ke Li

Doctoral Dissertations

"Antibody drug conjugates (ADCs) are emerging therapeutic products specially designed for the treatment of cancers. Potent cytotoxic agents are linked to antibodies via linkers. Antibody drug conjugates, which take advantage of both antibodies and cytotoxic agents, showed high selectivity towards cancer cells. Cytotoxic agents are delivered to the cancer cells selectively and kill them from inside while leaving low or non-toxicity towards normal cells. Antibody drug conjugates are actually heterogeneous mixtures. The major heterogeneities mainly lie in the drug to antibody ratio (DAR) and drug linking positions, both of which potentially affect the therapeutic index of ADCs. In this research, …

Designing Novel Multinary Transition Metal Selenides As High-Efficiency Oxygen Evolution Reaction Electrocatalysts And Investigating Surface Properties, Xi Cao

Doctoral Dissertations

”Water splitting has been widely considered to be an efficient way to generate sustainable and renewable energy resources in fuel cells, metal-air batteries and other energy conversion devices. Exploring efficient electrocatalysts to expedite the anodic oxygen evolution reaction (OER) is a crucial task that needs to be addressed to boost the practical application of water splitting. This research focuses on the identification of OER electrocatalysts by systematically designing non-stochiometric mixed transition metal-based selenide OER electrocatalysts through combinatorial electrodeposition and investigation of selenide-based naturally occurring minerals as effective OER electrocatalyst. Paper I describes the study of Ni-Fe-Co selenides as OER catalysts …

Three-Dimensional Nanotube Arrays For Solar Energy Harvesting And Production Of Solar Fuels, Wipula P. R. Liyanage

Doctoral Dissertations

"Over the past decade extensive research has been carried out on photovoltaic semiconductors to provide a solution towards a renewable energy future. Fabricating high-efficiency photovoltaic devices largely rely on nanostructuring the photoabsorber layers due to the ability of improving photoabsorption, photocurrent generation and transport in nanometer scale. Vertically aligned, highly uniform nanorods and nanowire arrays for solar energy conversion have been explored as potential candidates for solar energy conversion and solar-fuel generation owing to their enhanced photoconversion efficiencies.

However, controlled fabrication of nanorod and especially nanotube arrays with uniform size and shape and a pre-determined distribution density is still a …

The Benefit Of Precise Chemical Shift And Concentration Referencing In Nmr Applications, Ming Huang

Doctoral Dissertations

“In Nuclear Magnetic Resonance (NMR) spectroscopy, the chemical shift and intensity of NMR signals provide critical information about a sample's molecular structure, reaction conditions, and material properties. For the precise determination of structures and properties, it is critical to know sample or reaction conditions such as temperature, pH, concentration, or absolute amount of material. Chemical-shift and signal-intensity calibrations play a key role for extracting the maximum amount of information from NMR experiments. In this dissertation, internal and external reference standards are used to calibrate NMR spectra with respect to chemical shift and signal intensity. Sealed capillary tubes filled with specific …

Development And Demonstration Of Sampling Techniques For A Chirped Pulse Fourier Transform Microwave Spectrometer, Frank Edward Marshall

Doctoral Dissertations

"With the introduction of the Chirped Pulse-Fourier Transform Microwave Spectrometer in the past decade, it has become possible to rapidly study the rotational spectra of molecules in the gas phase. It is possible to study molecules that are not normally in the gas phase through the use of various sourcing techniques. The development of both the heated nozzle and the laser ablation sourcing techniques allow for the study of liquids and solids, respectively. The design and performance of these sources will be presented in detail and discussed. Additionally, the development of a Multi-Antennae detection scheme, useful in improving overall sensitivity …