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Mechanism And Kinetics Of Photocatalytic Partial Oxidation Of Methane On Single Site Mox Reaction Centers., Clint Evrard

Electronic Theses and Dissertations

Single-site transition-metal doped photocatalysts are a class of materials in which small transition-metal oxide clusters are embedded onto the surface of zeolites, graphene, and bulk semiconductors. Experimental findings demonstrate that VO4, CrO4, NbO4, and WO4 clusters embedded on an MCM- 41 mesoporous amorphous SiO2 are effective photocatalysts for oxidative reactions. The selective direct partial oxidation of methane (POM) to form methanol is essential for efficiently utilizing natural gas. Photocatalytic methane oxidation has advantages over traditional thermal catalysis as it can be deployed at small-scale facilities to reduce methane release into the atmosphere due to flaring potentially. Our work has aimed …

Remote Ambient Aerosols Found In The Southern Great Plains And Eastern North Atlantic: A Comprehensive Analysis Of Optical Behavior And Aerosol-Cloud Interaction, Daniel J. Bonanno

University of the Pacific Theses and Dissertations

The data presented in this thesis showcases the investigation of various aerosol types and the role they play in the hydrological system and global climate models. Long-range transport aerosols, including atmospheric soot, mineral dust, and ammonium sulfate, in addition to near-site sources such as secondary organic aerosols (SOAs), sea spray, aliphatic hydrocarbons, and other organics, are prioritized in the analysis of two separate remote field studies. Each of these campaigns revealed the juxtaposition between dry summer months and wet winter months, and the connection between seasonal variability and sample collection. Two spectromicroscopic techniques were used to elucidate chemical composition, morphology …

Spectroscopic Characterization Of Microhydration: Studying Molecular Properties, Acidity And Solvation In Ionic Water Clusters Using Cryogenic Infrared Vibrational Predissociation Spectroscopy, Sayoni Mitra

Yale Graduate School of Arts and Sciences Dissertations

Molecular level interactions give rise to the macroscopic chemical and physical properties of bulk electrolyte systems. A fundamental knowledge of these interactions facilitates understanding of this behavior and enables rational manipulation of the system at the molecular level. Among the experimental techniques, vibrational spectroscopy is widely used in several variations including linear absorption spectroscopy, ultrafast multidimensional spectroscopy, and interface specific spectroscopy. The advantage of using vibrational spectroscopy to study systems at the molecular level is its sensitivity towards structural information as well as relatively high time resolution. Standard solution phase and surface-sensitive spectroscopies, however, suffer from the drawback that the …

The Vagabond Flourine Atom Revisited: Dissociative Photoionization Of Tri- And Pentafluoropropene, Jessica K. De La Cruz

University of the Pacific Theses and Dissertations

Photoelectron Photoion Coincidence (PEPICO) Spectroscopy studies on two unsaturated hydrofluorocarbons (HFCs), also known as hydrofluoroolefines (HFOs), are presented here. Previously, the Sztáray group has studied the dissociation of trans-1,3,3,3-tetrafluoroprop-1-ene (ElixClean), which is a fourth-generation refrigerant and propellant and has lower global warming potential than its precursors. My study is an extension of the ElixClean study as it aims to explore how the different number of fluorine atoms impact the dissociation reactions of these molecules. Both 3,3,3-trifluoropropene (TFP) and cis-1,2,3,3,3- pentafluoropropene (PFP) are also utilized as propellants and refrigerants.Measurements were carried out with remote access to the CRF-PEPICO (combustion reactions followed …

Gas-Phase Acid-Base Properties And Conformations Of Oligopeptides Through Mass Spectrometry And Computational Studies, Yuntao Zhang

University of the Pacific Theses and Dissertations

This dissertation presents a comprehensive study of the peptides of interest to deeper understand the gas-phase acid-base properties in relation to their conformations and chirality. In the first part of the study, two pairs of alanine (A)-based isomeric peptides consisting of a basic probe, lysine (Lys) or 2,3-diaminopropionic acid (Dap), were investigated to understand the nature of the enhanced basicity when the basic probe was moved from the N-terminus to the C-terminus. In the second part of the study, alanine-based peptides containing a cysteine (C) as the acidic probe were investigated to understand the chirality effects on the gas-phase acidity …

Physical Chemistry, Ruth E. Stark

Open Educational Resources

This is a provisional syllabus for Physical Chemistry I (Thermodynamics), to be taught using an OER Textmap in Fall, 2021.

The Activity Of Abstraction In Physical Chemistry Problem Solving And Instruction, Jessica M. Karch

Graduate Doctoral Dissertations

Productive problem solving, concept construction, and sense making occur through the core process of abstraction. Although the capacity for domain-general abstraction is developed at a young age, the role of abstraction in increasingly complex and disciplinary environments, such as those encountered in undergraduate STEM education, is not well understood. Undergraduate physical chemistry relies particularly heavily on abstraction because it uses many overlapping and imperfect mathematical models to represent and interpret phenomena occurring on multiple scales. To reconcile these models, extract meaning from them, and recognize when to apply them in problem solving requires processes of abstraction. This dissertation aims to …

Identification Of New Pathways For Co Oxidation On Rh(111) & Spatial And Structural Control Of O-Induced Reconstruction Of Ag(111), Marie Turano

Dissertations

Understanding the fundamentals of oxygen surface structures under a variety of conditions is pivotal to determining reactivity of heterogeneous catalysis. Exposure of catalytically active metal surfaces to high oxygen coverages results in a myriad of surface structures. A further complication is the formation of subsurface oxygen (Osub) or oxygen present in the near subsurface region of the metal. It is known to form in transition metals yet the absorption of oxygen and resultant formation of Osub is not equivalent across all catalytically relevant metals. As a result, it is difficult to predict the stability and efficacy of the formation of …

Computational Elucidation Of The "Coloring Problem" In Rhenium Aluminum Silicon Compounds, Alec George Neeson

MSU Graduate Theses

Re₁Si₁Al₁ and its related compounds are potential thermoelectric materials. Previously, it was reported to adopt a MoSi₂-type structure with Si and Al atoms statistically sharing the same crystallographic sites. This recent study indicates otherwise – Si and Al are segregated and occupy different sites when mixed with a 1:1:1 stoichiometry. To confirm and rationalize the segregation between Si and Al, this research studied this compound with first-principle calculations. Several model structures have been constructed for Re₁Si₁Al₁ including a number of different super-cell models. Energy analysis confirmed that the …

Parahydrogen Hyperpolarized Multi-Nuclear Contrast Agents For Potential Mri Applications, Nuwandi Maduranga Ariyasingha Uragoda Wiyannalage

Wayne State University Dissertations

ABSTRACT

PARAHYDROGEN HYPERPOLARIZED MULTI-NUCLEAR CONTRAST AGENTS FOR POTENTIAL MRI APPLICATIONS

by

NUWANDI M. ARIYASINGHA

December 2020

Advisor: Dr. Eduard Chekmenev

Major: Chemistry (Physical)

Degree: Doctor of Philosophy

There have been numerous studies to develop fast, cost effective hyperpolaried (HP) contrast agents with higher polarization values that can be potentially employed for magnetic resonance clinical imaging. Some of the currently used contrast agents are based on 129Xe hyperpolarized nucleus. However, one of the problems associated with this approach, is the high cost of the produced hyperpolarized contrast agents. In addition, the other important practical problem is that the currently used clinical …

Instrument And Application Development In Saturation Recovery And Rapid Scan Electron Paramagnetic Resonance, Joseph E. Mcpeak

Electronic Theses and Dissertations

Enhanced signal sensitivity by the use of Rapid Scan (RS) electron paramagnetic resonance (EPR), a technique that allows for much faster magnetic field scans than traditional field-swept techniques, has facilitated improved data acquisition for many types of samples. For example, irradiated fingernails for radiation dosimetry have been studied using RS-EPR, which resulted in substantial decreases in detection limits. Samarium-mediated reduction mechanisms in organic synthesis have been investigated by RS-EPR providing evidence for a radical intermediate. Spectra of organic radicals exhibiting both narrow lines and closely spaced hyperfine interactions have been recorded via RS-EPR. Well-resolved spectra can be recorded at a …

The Investigation Of Methylidyne Radical (Ch) Reactions With Furan, 2-Methylfuran, And 2,5-Dimethlyfuran And The Photoionization And Photodissociation Of Valeric Acid, Erica Carrasco

Master's Theses

This thesis presents the combustion study of three furanic compounds using synchrotron radiation coupled with multiplexed photoionization mass spectrometry at 298 K. The experiments were performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source of the Lawrence Berkeley National Laboratory. The reactions of the three furanic compounds with methylidyne (CH) radicals were analyzed based on their photoionization spectra and kinetic profiles.

Additionally, the unimolecular dissociation of valeric acid was also studied and presented in this work using the double imaging photoelectron photoion spectrometry (i2PEPICO) coupled with synchrotron radiation from the VUV beamline. The experiments were carried out …

PdmsStar-Peg Hydrogels Prepared Via Solvent-Induced Phase Separation (Sips) And Their Potential Utility As Tissue Engineering Scaffolds, B. M. Bailey, R. Fei, Dany J. Munoz Pinto, M. S. Hahn, M. A. Grunlan

Dany J. Munoz Pinto

Inorganic-organic hydrogels based on methacrylated star polydimethylsiloxane (PDMS_star-MA) and diacrylated poly(ethylene glycol) (PEG-DA) macromers were prepared via solvent-induced phase separation (SIPS). The macromers were combined in a dichloromethane precursor solution and sequentially photopolymerized, dried and hydrated. The chemical and physical properties of the hydrogels were further tailored by varying the number average molecular weight (M_n) of PEG-DA (M_n = 3.4k and 6k g mol^-1) as well as the weight percent ratio of PDMS_star-MA (M_n = 7k g mol^-1) to PEG-DA from 0:100 to 20:80. Compared to analogous hydrogels …

Modeling Cell Line-Specific Recruitment Of Signaling Proteins To The Insulin-Like Growth Factor 1 Receptor, Keesha E. Erickson, Dipak Barua, For Full List Of Authors, See Publisher's Website.

Chemical and Biochemical Engineering Faculty Research & Creative Works

Receptor tyrosine kinases (RTKs) typically contain multiple autophosphorylation sites in their cytoplasmic domains. Once activated, these autophosphorylation sites can recruit downstream signaling proteins containing Src homology 2 (SH2) and phosphotyrosine-binding (PTB) domains, which recognize phosphotyrosine-containing short linear motifs (SLiMs). These domains and SLiMs have polyspecific or promiscuous binding activities. Thus, multiple signaling proteins may compete for binding to a common SLiM and vice versa. To investigate the effects of competition on RTK signaling, we used a rule-based modeling approach to develop and analyze models for ligand-induced recruitment of SH2/PTB domain-containing proteins to autophosphorylation sites in the insulin-like growth factor 1 …

Characterization Of Hydrogen Bonding, Halogen Bonding And Argyrophilic Interactions Using Computational Modeling, Sarah Nicole Arradondo

Electronic Theses and Dissertations

Non-covalent interactions govern multiple important chemical processes throughout nature from those within the human body to the complex environment of the atmosphere. Quantum mechanical electronic structure modeling of these relatively weak interactions can provide molecular level insight that can further our understanding of specific macroscopic properties. In the present work different non-covalent interactions are computationally evaluated within four systems. A small prototypical hydrogen bonded system and the various structural motifs that promoted proton transfer within concentrated acid and water clusters are characterized with sophisticated wavefunction based methods and large robust basis sets in order to accurately predict the structures energies …

Roaming Transition States And Highly Accurate Thermochemistry: A Pepico Study Of Two Small Combustion Systems, Kyle John Covert

University of the Pacific Theses and Dissertations

Two small combustion systems, methyl hydroperoxide (CH₃OOH) and 2-propanol ((CH₃)₂CHOH), were studied using imaging photoelectron photoion coincidence spectroscopy (iPEPICO), which combines photoelectron spectroscopy and photoionization mass spectrometry to detect coincident photoelectron-photoion pairs. In the photon energy range of 11.4–14.0 eV, energy selected CH₃OOH⁺ ions dissociate into CH₂OOH⁺, HCO⁺, CH₃⁺, and H₃O⁺ ions. The lowest-energy dissociation channel is the formation of the cation of the smallest “QOOH” radical, CH₂OOH⁺. A statistical rate model fitted to the …

I3: Isomerization Of Isomer Ions, Krisztián Gabor Torma

University of the Pacific Theses and Dissertations

Photoelectron Photoion Coincidence (PEPICO) spectroscopy is a robust tool for elucidating complex unimolecular dissociation mechanisms and for determining thermochemical and kinetic data of gas-phase ion dissociations with high accuracy. In this work, the dissociative photoionization of two sets of isomeric systems were analyzed with PEPICO: 1) C7H7+ ions of toluene (Tol) and 1,3,5-cycloheptatriene (CHT), and 2) two butyl alcohol isomers, 1-butanol and isobutanol. Threshold dissociative photoionization data on these four molecules of interest were collected on the imaging PEPICO apparatus at the VUV beamline of the Swiss Light Source. Data analysis was aided by ab initio calculations and Rice-Ramsperger-Kassel-Marcus (RRKM) …

Steric Effects Of Alkyl Ammonium Salts On The Combustion Of Exchanged Smectite Clays, Celeste A. Keith

Electronic Theses and Dissertations

Bomb calorimetry was explored as a new method for determining the cation exchange capacity (CEC) of clays. Smectite clays were modified with several alkyl ammonium salts varying in number of carbons and the spatial orientation of the carbons about the central nitrogen atom. The clays used, standards purchased from the Source Clay Repository, have CECs of 44, 80, 88, and 120 meq/100 g. Theoretically, the combustion energy of the organo-clays should be approximately the same for each salt. Any differences in energy would be due to the different structures of the salts and how they are oriented in the interlamellar …

Carbon Nanotube Yarn Based Dye Sensitized Solar Cells With Enhanced Electron/Hole Pair Recombination Prevention Characteristics, Glenn E. Grissom

Theses and Dissertations

Carbon nanotube yarn based solar cells (CNTYSCs) show promise in a variety of applications such as military and smart fabrics. We use a highly aligned and interwoven Carbon nanotube yarn (CNTY) for the working electrode (WE) and counter electrode (CE), to create a flexible super strong, conductive, and photo active surface for the support of a calcined TiO2 nano-solution and macro-solution deposition as a base for added functionalizations of a dye-sensitized solar cell (DSSC) that is able to maintain its flexibility and integrity. The CNT fiber based solar cells have power conversion ability that is independent of the direction of …

Physical Chemistry Of Gas-Liquid Interfaces: Foreword, Jennifer Faust

All Faculty Articles

Physical Chemistry of Gas-Liquid Interfaces, the first volume in the Developments in Physical & Theoretical Chemistry series, addresses the physical chemistry of gas transport and reactions across liquid surfaces. Gas-liquid interfaces are all around us, especially within atmospheric systems such as sea spray aerosols, cloud droplets, and the surface of the ocean. Because the reaction environment at liquid surfaces is completely unlike bulk gas or bulk liquid, chemists must readjust their conceptual framework when entering this field. This book provides the necessary background in thermodynamics and computational and experimental techniques for scientists to obtain a thorough understanding of the …

Computational Methods In Biomolecules:Study Of Hydrophilic Interactions In Protein Folding & Constant-Ph Molecular Simulation Of Ph Sensitive Lipid Morc16, Wei Zhang

University of the Pacific Theses and Dissertations

Water molecules play a significant role in biological process and are directly involved with bio-molecules and organic compounds and ions. Recent research has focused on the thermal dynamics and kinetics of water molecules in solution, including experimental (infrared spectroscopy and Raman spectroscopy) and computational (Quantum Mechanics and Molecular Dynamics) approaches. The reason that water molecules are so unique, why they have such a profound influence on bio-activity, why water molecules show some anomalies compared to other small molecules, and where and how water molecules exert their influence on solutes are some of the areas under study. We studied some properties …

Atomistic Insights Into Photoprotein Formation: Computational Prediction Of The Properties Of Coelenterazine And Oxygen Binding In Obelin, Thomas M. Griffiths

University of Wollongong Thesis Collection 2017+

Bioluminescence in marine systems is dominated by the use of one ligand for light production, coelenterazine. The bioluminescent reaction of coelenterazine is an enzyme catalysed, oxidative decarboxylation. During the reaction coelenterazine reacts with molecular oxygen to form carbon dioxide, coelenteramide and light. One such class of bioluminescent systems is the Ca[sup]2+-regulated photoproteins. These proteins, rather than continuously processing substrate, bind 2-hydroperoxycoelenterazine as an intermediate along the reaction pathway. The reaction is halted here until an external stimulus triggers the continuation of the bioluminescent reaction. There are currently no reported experimental, atomistic descriptions of the states that lead to this ternary …

Optical Studies Of The Solution Phase Reduction And Stabilization Of Indigo Tetrasulfonate In Polyelectrolyte Complexes, Becca Hoene, Dion Rivera

All Faculty Scholarship for the College of the Sciences

Ultraviolet-visible (UV-vis) and fluorescence spectroscopy have been used to characterize the polyelectrolyte complexes (PECs) formed when potassium indigo tetrasulfonate (ITS) interacts with poly diallydimethylammonium chloride (PDADMAC) through columbic attraction in the presence of the reducing agent sodium bisulfite, NaHSO3. The PDADMAC facilitates both the reduction of the ITS and the stabilization of the reduced state of the ITS in an atmospheric oxygen environment. Dilutions of the dye solution show that the PEC is stable to dilutions of at least 1 to 1000. UV–vis studies indicate that the reduced ITS (ITSred) forms what is likely a J-aggregate in the presence of …

Reactivity Of Ketyl And Acetyl Radicals From Direct Solar Actinic Photolysis Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The variable composition of secondary organic aerosols (SOA) contributes to the large uncertainty for predicting radiative forcing. A better understanding of the reaction mechanisms leading to aerosol formation such as for the photochemical reaction of aqueous pyruvic acid (PA) at λ ≥ 305 nm can contribute to constrain these uncertainties. Herein, the photochemistry of aqueous PA (5-300 mM) continuously sparged with air is re-examined in the laboratory under comparable irradiance at 38° N at noon on a summer day. Several analytical methods are employed to monitor the time series of the reaction, including (1) the derivatization of carbonyl (C═O) functional …

Derivatization Of Diimine Tricarbonyl Re(I) Complexes For Cooperative Catalysis And Surface Immobilization, Michael Eric Louis

Doctoral Dissertations

Carbon dioxide (CO2) is a known greenhouse gas and in recent years has been identified as one of the primary contributors to changes in global climate. Nature utilizes CO2 through photosynthesis in which the plants harness energy from the sun to extract electrons from water to convert CO2 into sugars to fuel cellular activities. Using this as inspiration, our research aims to photochemically convert CO2 to higher value products by designing appropriate catalytic systems. Diimine-tricarbonyl rhenium compounds have demonstrated excellent activity in photo and electrochemical CO2 reduction. A low-energy pathway has been postulated in which Re(I)-based catalysts mediate CO2 reduction …

Fragment-Based Excitonic Coupled-Cluster Theory For Large Chemical Systems, Yuhong Liu

University of the Pacific Theses and Dissertations

Accurate energetic modeling of large molecular systems is always desired by chemists. For example, ligand-protein binding simulations and enzymatic catalysis studies all involve with a small energy difference. The energetic accuracy depends largely on a proper handling of electronic correlations. Molecular mechanics (MM) methods deliver a parameterized Newtonian treatment to these problems. They show great capability in handling large calculations but give only qualitatively good results. Quantum mechanics (QM) methods solve Schrödinger equations and exhibit much better energy accuracy, though the computational cost can be prohibitive if directly applied to very large systems.

Fragment-based methods have been developed to decompose …

Thermochemical Properties Of Fluorinated Hydrocarbons, Hydroperoxides, And Fluorinated Hydroperoxides; Thermochemistry And Kinetics On Dissociation And Association Reactions Of Oxiranyl Radical, Heng Wang

Dissertations

Thermochemical properties on fluorinated hydrocarbons, alcohol, hydroperoxides, and alkyl hydroperoxides are determined. Reaction kinetics and modeling on the three member ring cyclic ether radical, oxiranyl radical, are studied under atmospheric and combustion environments.

Molecular geometries, vibration frequencies, internal rotor potentials, and thermo-chemical properties (ΔfHº298, S°(T) and C°p(T)) for fluorinated-hydrocarbons, thermochemical properties and bond energies, for alkyl and fluoro hydroperoxides and fluoro alcohols are determined with comparison of data from a number of different ab initio, density functional theory (DFT) and composite calculation methods, and basis sets.

Kinetic parameters for unimolecular decomposition and isomerization reactions of the oxiranyl radical are determined …

Analysis Of Scientific Argumentation In Two Physical Chemistry Classrooms Using The Pogil Approach, Alena C. Moon

Open Access Dissertations

The benefits of facilitating argumentation in science education have been well reported (Jimenez-Aleixandre & Erduran, 2007). Engaging in argumentation has shown to model authentic scientific inquiry as well as promote development of content knowledge. However, less emphasis has been placed on facilitating argumentation in upper level undergraduate courses, though it is important for evaluating undergraduate curricula to characterize upper level students’ scientific reasoning. This work considers two implementations of the POGIL physical chemistry curriculum and evaluates the classroom argumentation. The researchers aimed to consider the content of the arguments and dialectical features characteristic of socially constructed arguments (Nielson, 2013). To …

Molecular Dynamics Simulations Of A Pentacene Derivative On Gold Surfaces In The Quantum Mechanical And Classical Mechanics Frameworks, Ryan Allen Miller

Master's Theses and Capstones

With increasing potential to serve as a basis for constructing organic photovoltaic de- vices, the directed self-assembly of small organic molecules on metal substrates provides an interesting new method of bottom-up device building. By utilizing the qualities inherent in the substrate and molecules, one can manipulate surface topology to create functional layers of molecules in a desired configuration. However, tailoring these organic layers in a useful way requires detailed analysis of the substructure characteristics. With top-down visualization approaches like Scanning Tunneling Microscopy (STM) pro- viding a limited view of assembled layer structural characteristics, molecular dynamics sim- ulations must be employed …

The Role Of Organic Matter In The Surface Chemistry Of Arsenic Compounds On Iron−(Oxyhydr)Oxides Studied By Atr-Ftir, Arthur Situm

Theses and Dissertations (Comprehensive)

The interaction of organic matter with the interfaces of active soil components such as iron oxides is ubiquitous within soil environments. The presence of organics at these interfaces may have implications for other soil constituents whose mobility is controlled by their ability to bind to active soil components. Most of the studies performed to date which look at these interactions are bulk/batch studies performed ex-situ. Attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized within this work to study interactions between select model organics (citrate, oxalate and pyrocatechol) and iron−(oxyhydr)oxides, as well as their effect on the surface …