Physical Sciences and Mathematics Commons^™

Knowledge Management Of Historical Data: Ontology Development For Chemical Reactions, Quynh D. Tran, Alexander Harding Bradley, Balashanmuga Priyan Rajamohan, Jonathan E. Gordon, Van D. Tran, Kiefer Lin, Erika I. Barcelos, Laura S. Bruckman, Roger H. French

Researchers, Instructors, & Staff Scholarship

Knowledge management of the literature and historical data is critical to accelerated drug and materials discovery. Currently, literature knowledge is scattered in journal articles in various formats: diagrams, texts, plots, etc. Historical data from past experiments are saved in a number of local computers under confusing folder structures with ambiguous file names. To manage and organize historical data and knowledge, our group (SDLE) at CWRU follows FAIR (Findable, Accessible, Interoperable, Reusable) principles, which outline the best practices for data stewardship and data provenance, and ontology, a formal representation of terms and concepts and their relationships, as a tool to improve …

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Applications For Metabolomics, Darcy Cochran, Robert Powers

Robert Powers Publications

Metabolomics is an interdisciplinary field that aims to study all metabolites < 1500 Da that are ubiquitously found within all organisms. Metabolomics is experiencing exponential growth and commonly relies on high-resolution mass spectrometry (HRMS). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is a form of HRMS that is particularly well suited for metabolomics research due to its exceptionally high resolution (10⁵–10⁶) and sensitivity with a mass accuracy in parts per billion (ppb). In this regard, FT-ICR-MS can provide valuable insights into the metabolomics analysis of complex biological systems due to unique capabilities such as the easy separation of isobaric and isomeric species, isotopic fine structure analysis, spatial resolution of metabolites in cells and tissues, and a high confidence (error) in metabolite identification. Alternatively, the large and complex data sets, long acquisition times, high cost, and limited access mainly through national mass spectrometry facilities may impede the …

Assessing The Reactivity Of Amino Acids To Chlorination Using Capillary Electrophoresis, Pedro De Allende

Electronic Theses, Projects, and Dissertations

Amino acids (AA) are ubiquitous in wastewater systems. One of the most popular wastewater treatments is chlorination which is effective at eradicating bacteria and overall treating the wastewater, but it can also produce disinfection by-products (DBPs). Certain DBPs have been classified as Class B Carcinogens to humans and are therefore highly regulated and monitored. Past studies have shown that natural organic matter (NOM), specifically amino acids, can be precursors to DBPs if chlorinated to the correct dose. This thesis project explored AA chlorination's mechanism(s) to understand further which products arise. In particular, the investigation detailed which steps of the mechanism …

Quantum Modeling & Experimental Studies Of Radical Chemistry, Justin Michael Barrett

Graduate Theses and Dissertations

This work describes two projects centered around radical chemical mechanisms. The first investigation generalized the utility of a C-N bond homolysis followed by a [1,3] – rearrangement synthetic strategy found possible in N-alkylated thiazole & benzothiazole species onto analogous systems. Computational investigation guided the inquiry on structurally analogous systems that would favor a radical, [1,3] – rearrangement. Herein, we describe the implementation of that mechanism to transform Breslow Intermediate-like substrates into tertiary alcohol and amide products under facile conditions. We confer on the proficiency of this strategy with 2-pyridinemethanol and the problematic implementation with 2-(aminomethyl)pyridine. The second investigation solved a …

Investigating The Applications Of Peps To The Measurement Of The Stabilities Of Staphylococcal Nuclease (Stw) And Human Acidic Fibroblast Growth Factor (Hfgf1), Motolani Omolade Matthew

Graduate Theses and Dissertations

This dissertation presents a detailed investigation into the applications of Protein Equilibrium Population Snapshot H/D Exchange Electrospray Ionization Mass Spectrometry (PEPS-H/D exchange or PEPS) method. This method is based on protein equilibrium unfolding, and its fundamental capability is to capture a "snapshot" of the protein's state, allowing us to monitor the ratio of the unfolded to folded populations at different chemical denaturant concentrations. First, to increase the accuracy of PEPS data analysis for assessing protein stability, the traditional linear extrapolation method (LEM) was replaced. Instead of using LEM, which calculates free energy change based on the peak ratio of unfolded …

Metal Assisted O2-Dependent Carbon-Carbon Bond Cleavage Of Β-Diketones And Flavonols, Stephen N. Anderson

All Graduate Theses and Dissertations, Fall 2023 to Present

Almost everything we interact with on a daily basis has been synthesized by chemists ranging from plastics, food preservatives, and medications. The diversity of synthetic molecules are achieved by the formation of new bonds between existing molecules and/or through the cleaving of bonds found in a molecule. There are uncountable amount of conditions reported to facilitate chemical reactions which all depend on the nature of molecules being used and the environment it is used in.

In recent years, more attention has been paid to identify chemical reactions that can use more environmentally favorable conditions and reduce the use of limited …

Functional Electrolytes Designing And Studying For Lithium Metal And Non-Aqueous Zinc Metal Batteries, Liping Zhang

All Graduate Theses and Dissertations, Fall 2023 to Present

Our current energy policy relies heavily on burning fossil fuels, raising serious concerns due to CO₂-related global warming. Consequently, significant progress is being made in pursuing renewable and green energy sources, such as solar, wind, and geothermal energy. These renewable energies require rechargeable batteries as energy storage systems to compensate for their intermittent nature.

Over the decades, lithium-ion batteries (LIBs) have become the dominant power sources for portable electronic devices. Current LIBs rely on graphite anodes with a limited theoretical capacity (372 mAh g^-1), which restricts their advanced applications. Li metal (Li⁰) anodes, with …

Multiscale Modeling Of Morphology And Proton/Ion Transport In Electrolytes, Zhenghao Zhu

Doctoral Dissertations

Understanding structure-function relationships in electrolytes is essential for advancing energy conversion and storage. This dissertation employs multiscale modeling and simulations to study the morphology and proton/ion transport in various electrolytes for electrochemical systems, including anion exchange membranes (AEMs), protic ionic liquids (PILs), pure phosphoric acid (PA) and aqueous acid solutions, ionic liquids (ILs), and polymerized ionic liquids (polyILs).

Mesoscale dissipative particle dynamics (DPD) simulations were employed to study the hydrated morphology of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS)-based AEMs. The results indicate that the choice of the functional group moderately affects the water distribution and has little influence on the …

Investigation Of Molecular Transition Metal Complexes: Structures, Magnetic Properties, And Reactivities, Adam T. Hand

Doctoral Dissertations

The dissertation describes the work on transition metal complexes to determine their structures, magnetic properties, and reactivities. Molecular magnetic complexes containing one cobalt(II) or rhenium(IV) ion have been studied to obtain their characteristic zero-field splittings and spin-phonon couplings by magnetometry and advanced spectroscopies. The investigation of spin relaxation and phonon features gives insight into potential magnetic relaxation mechanisms. Studies by ligand field theory, including ab initio ligand-field analysis, show how coordination environments of the metal centers affect the magnetic properties. Through the analyses, the impact of the coordination geometry/symmetry on the zero-field splittings can be explained. Such understanding of magneto-structural …

Single Charge Carrier Dynamics In A Single Polymer Chain, Ming Lei

All Dissertations

Understanding how charge carrier move through conjugated polymers is crucial for optimizing the functionality and efficiency of various applications, from organic solar cells and light-emitting diodes (LEDs) to field-effect transistors. Previous studies have demonstrated that tracking the fluorescence centroid displacement provides a method to determine the position of single charge carriers in a conjugated polymer nanoparticle. This method allows the observation of charge carrier trajectories over time and allow researchers to obtain insights into the dynamic processes. In addition, a detailed map of the energy landscape can be constructed by analyzing the fluorescence spectrum. These techniques were previously applied to …

Assessment Of Tce And Chiral Pcb Dechlorination Rate, Congener Diversity, And Enantioselectivity In Town Creek, Sc, Usa Sediment Microcosms, Catherine P. Sumner

All Dissertations

Polychlorinated biphenyls (PCBs) and trichloroethene (TCE) are ubiquitous contaminants and are recognized as persistent organic pollutants due to their extreme chemical stability. PCBs were manufactured by chlorinating biphenyls that created 209 congeners with various structures, of which 19 are chiral and can exist as a pair of stable atropisomers. PCBs have been known to cause developmental and neurological toxicity in humans and wildlife; they can act as endocrine disrupters, carcinogens, and teratogens. Sangamo Weston Inc. was an industrial plant located near Town Creek in Pickens Country, South Carolina, that manufactured capacitors and used Aroclors 1016 and 1254 as dialectic fluids …

Data Driven Acceleration Of Coupled-Cluster Calculations Using Machine Learning, Multitask Learning And Physics Imposed Learning, Perera Don Varuna Sanjaya Pathirage

Doctoral Dissertations

Data-driven coupled-cluster singles and doubles (DDCCSD) method developed by Townsend and Vogiatzis aims at predicting the coupled-cluster t₂ amplitudes using MP2-level electronic structure data with machine learning. In this work we address limitations of the DDCCSD method to expand the applicability and increase the accuracy. First, we implement localized molecular orbitals (LMO) to the DDCCSD method. There is a ten-fold increase in accuracy when the LMO implementation is used compared to the canonical molecular orbital implementation. Next, we introduced five data selection techniques to select data for testing and training. Here we were able to achieve accuracies less than …

Design Of Engineered Nanomaterials For Pfas Adsorption And Catalytic Degradation From Relevant Environmental Conditions, Sheng Yin

Open Access Theses & Dissertations

Poly- and per-fluoroalkyl substances (PFAS) are a class of artificially made chemicals whose carbon chains are fully or partially fluorinated. Due to their persistent and pervasive distribution and their adverse effects on human health, the removal of PFAS from the environment has been the focus of current research. This project explores the use of engineered nanomaterials for the effective removal of PFAS through various adsorption and catalytic degradation methods. First, a comprehensive review of recent studies highlights the significant potential of various nanomaterials, including carbon-based, non-metal, single-metal, and multi-metal nanomaterials, for PFAS remediation. These materials are evaluated for their performance, …

Method Development For The Quantification Of Critically Valuable Elements In Permian Basin Produced Waters, Carley Oliver

Open Access Theses & Dissertations

Produced waters (PW) are a major byproduct of the oil and gas industrial hydraulic fracturing processes that create a major waste disposal issue with a need for disposal, treatment, and reuse method developments. The current primary disposal method is subsurface injection, which can lead to high pressures in the subsurface. PWs are often highly saline from mineral leaching due to long residence in subsurface reservoirs. According to the USGS National Minerals Information Center, bromine, calcium chloride, iodine, lithium, magnesium, and sodium chloride have been found in and extracted from these domestic subsurface brines, suggesting that there may be other economically …

Application Of Functionalized Organosilicas In Adsorption Of Nitrates, Stephen Amoako

Electronic Theses and Dissertations

This study addresses the critical environmental issue of elevated nitrate levels in water bodies, primarily due to excessive use of nitrogenous fertilizers and improper waste disposal. It focuses on reducing nitrate concentrations in polluted water to permissible levels through the effectiveness of hybrid materials in nitrate adsorption. We synthesized nine amino-functionalized adsorbents using grafting and sol-gel techniques. Batch adsorption tests confirmed the high nitrate adsorption capacities of these adsorbents, with sol-gel materials showing the highest efficiency due to their abundant amino group contents. Among these, the surfactant-free, sol-gel adsorbent was the most effective, combining ease of synthesis with cost-efficiency. Our …

Studies Of Exotic Electronic, Optical, And Electrochemical Properties In Nanoparticle Assembly And Graphene, Jay Min Lim

Department of Mechanical and Materials Engineering: Dissertations, Theses, and Student Research

It is well known that exotic properties and phenomena emerge as structural dimensions shrink to nanoscales. We self-assembled one-dimensional chains of gold nanoparticles in solution and quantified the growth process by monitoring the redshift of localized surface plasmon resonance (LSPR). Curiously, the redshift stopped while the chains continued to rearrange as manifested by gradual reduction in the LSPR peak. Using electromagnetic simulations, we quantitatively explained the phenomena as a rapid “addition-polymerization” followed by a sharp transition to “condensation-process.” Next, recognizing the significant electric field enhancement in the interparticle gap, a photoluminescent-active Eu³⁺ ion was used to probe Surface-Enhanced Photoluminescence …

High-Resolution Ion Mobility Analysis Of Isomeric Bile Acids Using Structures For Lossless Ion Manipulations (Slim) Im-Ms, Emmaleigh D. Efird

All Theses

Bile acids are an essential part of the human digestion system and play an important role in lipid absorption, bacteria movement in the small intestine, and regulation of the farnesoid X receptor (FXR) and G protein-coupled bile acid receptors (GPBAR) responsible for homeostasis. They are synthesized in the liver, stored in the gallbladder and the excess is carried on to the small intestine. Many liver and intestinal diseases are diagnosed based on bile acid metabolism pathways and the structures of those bile acids. Therefore, the bile acid structure determines the function of the molecule. Many bile acids are similar in …

Investigating Liquid-Liquid Phase Separation In Lipid Bilayers: A Multi-Modal Approach Utilizing Spectroscopy, Microscopy, And Cryo-Em, Karan D. Sharma

Doctoral Dissertations

This thesis explores the characterization of liquid-liquid phase separation in model lipid bilayers using fluorescence, optical microscopy, and cryo-electron microscopy (cryo-EM) integrated with machine learning (ML) analysis. The plasma membrane has a complex composition, lateral heterogeneity and dynamic structure which makes it challenging to study. Simplified model membranes containing three or four-component lipid mixtures, typically comprising low- and high-melting lipids along with cholesterol, form phase separated systems that mimic lateral heterogeneity/lipid rafts in biomembranes. In living cells, lipid rafts are thought to form nanoscopic domains smaller than 200 nm. These domains cannot be resolved by conventional optical microscopy. For a …

Molecule-Based Quantum Materials Under Extreme Conditions, Avery Leon Blockmon

Doctoral Dissertations

Molecule-based quantum materials are a class of compounds with competition between the spin, orbitals, charge, and lattice. They feature flexible architectures and structural designs that can be easily modified for different functionalities. As a result of their overall low energy scales, they can be easily tuned with external stimuli like magnetic field or pressure to reveal new states and properties. This dissertation presents a high magnetic field investigation of three different molecule-based quantum materials under extreme conditions revealing insights into their structural, electronic, and magnetic properties.

My initial study analyzes decoherence pathways in spin qubit Na₉[Ho(W₅O …

Evolution Mechanism Of Organic Macromolecular Structure During Lignite Pyrolysis, Ying Shi, Yanming Zhu, Zhenjiang You, Wu Li, Yang Wang, Yu Song

Research outputs 2022 to 2026

Understanding the mechanisms governing coal pyrolysis reactions, particularly in relation to the coal macromolecular structure, is crucial for improving energy efficiency and facilitating the transition of coal into a clean energy source. This study employs cutting-edge techniques, such as High-Resolution Transmission Electron Microscopy (HRTEM) and Thermogravimetric Analysis coupled with Fourier Transform Infrared Spectroscopy and Mass Spectrometry (TG–FTIR–MS), to analyze lignite and its residual solid samples subjected to pyrolysis across a range of temperatures from 300 °C to 1100 °C. The variational characteristics of the macromolecular structure during coal pyrolysis are examined. Utilizing molecular dynamics simulations, we analyze the evolution mechanism …

Extraction Of Neutron-Gamma Irradiated Diffusion Pump Oils, Cooper L. Tillman

All Theses

This work successfully demonstrates solvent extraction methods for separation of oil from the by-products when two commercially available vacuum pump oils were exposed to an intense neutron and gamma-ray radiation environment. Nuclear fusion power at a commercial scale has accelerated the need for radiation resistant vacuum technology, such as oil-based diffusion pumps. Polyphenyl ether and aromatic silicone oils were irradiated at the Rhode Island Nuclear Science Center (RINSC) up to MGy absorbed doses with neutron and gamma-ray radiation. Solvent extractions were performed using hexane and isopropanol to characterize the oil extraction as a function of total absorbed dose. The by-products …

Phthalocyanine-Enabled Technologies For Water Treatment And Disinfection Strategies, Hooralain Bushnaq, Catherine Munro, Sisi Pu, Amir Razmjou, Masoumeh Zargar, Giovanni Palmisano, Srinivas Mettu, Ludovic F. Dumée

Research outputs 2022 to 2026

Water treatment and disinfection are critical factors in ensuring a safe and sustainable water supply. Phthalocyanines (Pcs), a class of versatile and robust organic compounds, have garnered significant attention for their application in various water treatment processes. This review paper offers a groundbreaking investigation of Pc-enabled technologies within the domain of water treatment applications. The core aim of this review is to meticulously analyze the chemical and optical properties of Pcs, elucidate their photosensitization mechanism and establish the crucial connection between their chemical structure and photodynamic efficacy. The various modes of Pcs application in water treatment processes - whether in …

Catalytic Hydrogenation Of Co2 In Water And Ionic Liquids Using Platinum On Carbon, Kristin Collins

Masters Theses & Specialist Projects

Platinum-on-carbon (Pt/C) is a commercially-available catalyst that has been used in the literature to benchmark the performance of catalysts produced using platinum/cobalt alloy nanoparticles. Initially, we intended to build upon this example by synthesizing shape-controlled platinum/cobalt alloy nanoparticles in ionic liquids and compare their ability to catalyze the hydrogenation of CO₂ to methanol against Pt/C as a benchmark, with the idea that ionic liquids may improve catalysis. However, we found that Pt/C was unable to catalyze the hydrogenation of CO₂ to methanol. In an attempt to track the source of this discrepancy, Pt/C was characterized using thermogravimetric analysis …

Di­Chlorido­Tetra­Kis­(3-Meth­­Oxy­Aniline)Nickel(Ii), Benjamin A. Mukda, Mark M. Turnbull

Chemistry

The reaction of nickel(II) chloride with 3-meth­oxy­aniline yielded di­chlorido­tetra­kis­(3-meth­oxy­aniline)nickel(II), [NiCl₂(C₇H₉NO)₄], as yellow crystals. The Ni^II ion is pseudo-octa­hedral with the chloride ions trans to each other. The four 3-meth­oxy­aniline ligands differ primarily due to different conformations about the Ni—N bond, which also affect the hydrogen bonding. Inter­molecular N—H⋯ Cl hydrogen bonds and short Cl⋯Cl contacts between mol­ecules link them into chains parallel to the b axis.

Excited State Processes In Radical Elaborated Platinum Donor-Acceptor Complexes, Sangita Paudel

Chemistry and Chemical Biology ETDs

Organo-transition metal complexes are being widely studied to understand their photophysical properties for their wide range of applications as efficient emitters in organic light emitting diodes (OLEDs), light emitting electrochemical cells (LEECs), etc. Cyclometalated organo-transition metal complexes such as cyclometalated square planar platinum(II) complexes are becoming suitable candidates for such applications because of their highly efficient luminescence. Understanding the excited properties of such complexes is useful in designing highly efficient and color tunable phosphors with desired excited state lifetimes. We aim to explore the influence of radical substituents on electronic structure, luminescence quantum efficiencies, and excited state lifetimes by synthesizing …

We Think, We Smell, We Remember: The Effect Of Smell On Memory For Chemistry Lab Learning, Michael A. Marino, Francine Wisnewski, Catherine Reilly, Andre Alexis

Faculty Presentations: BCES

The traditional five senses are the primary receptors of external stimuli for the brain. While tactile learning and visual observations are integral to the chemistry laboratory, olfaction is a sense that should be considered part of an educator's repertoire. Previous studies have discovered that our sense of smell plays a significant role in triggering memories. Moreover, specific scents like vanillin can prompt anamneses to recall previous experiences. A sample of 61 college students was employed for a three-week pretest-posttest control group experimental design. In the first week, participants conducted a chemical reaction to synthesize isoamyl acetate, the familiar and nontoxic …

Professor Yong Yang, The Editorial Board Member Of Journal Of Electrochemistry, Is Elected As A Fellow Of The Electrochemical Society, Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.

Series Reports (1/4): Advancements In Electrochemical Energy Conversions At Prof Wei’S Group Of Chongqing University: High-Performance Oxygen Reduction Catalysts For Fuel Cells, Fa-Dong Chen, Zhuo-Yang Xie, Meng-Ting Li, Si-Guo Chen, Wei Ding, Li Li, Jing Li, Zi-Dong Wei

Journal of Electrochemistry

Two major challenges, high cost and short lifespan, have been hindering the commercialization process of low-temperature fuel cells. Professor Wei’s group has been focusing on decreasing cathode Pt loadings without losses of activity and durability, and their research advances in this area over the past three decades are briefly reviewed herein. Regarding the Pt-based catalysts and the low Pt usage, they have firstly tried to clarify the degradation mechanism of Pt/C catalysts, and then demonstrated that the activity and stability could be improved by three strategies: regulating the nanostructures of the active sites, enhancing the effects of support materials, and …

Data-Driven Viewpoint For Developing Next-Generation Mg-Ion Solid-State Electrolytes, Fang-Ling Yang, Ryuhei Sato, Eric Jian-Feng Cheng, Kazuaki Kisu, Qian Wang, Xue Jia, Shin-Ichi Orimo, Hao Li

Journal of Electrochemistry

Magnesium (Mg) is a promising alternative to lithium (Li) in solid-state batteries due to its abundance and high theoretical volumetric capacity. However, the sluggish Mg-ion conduction in the lattice of solid-state electrolytes (SSEs) is one of the key challenges that hamper the development of Mg-ion solid-state batteries. Though various Mg-ion SSEs have been reported in recent years, key insights are hard to be derived from a single literature report. Besides, the structure-performance relationships of Mg-ion SSEs need to be further unraveled to provide a more precise design guideline for SSEs. In this Viewpoints article, we analyze the structural characteristics of …

Kai Wu, The Editorial Board Member Of Journal Of Electrochemistry And Chief Scientist Of Catl, Receives The National Science And Technology Progress Award, Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.