Physics Commons^™

Optimization Of Useful Hard X-Ray Photochemistry, David Lewis Goldberger

UNLV Theses, Dissertations, Professional Papers, and Capstones

X-ray induced damage is generally considered a nuisance, but in the field of Useful Hard X-ray Photochemistry we harness the highly ionizing and penetrating properties of hard X-rays (> 7 keV) to initiate novel photochemical decomposition and synthesis at ambient and extreme conditions. Preliminary experiments suggest that the energy of irradiating photons and the sample pressure play roles in determining the nature of X-ray induced damage. Here, we present the X-ray energy dependence of damage induced in strontium oxalate, strontium nitrate, and barium nitrate, as well as the pressure dependence of X-ray induced damage of strontium oxalate. Our results indicate …

Nmr Characterizations Of Candidate Battery Electrolytes, Stephen A. Munoz

Dissertations, Theses, and Capstone Projects

Enormous strides have been made in next-generation power sources to build a more sustainable society. Energy storage has become a limiting factor in our progress, and there are huge environmental and financial incentives to find the next step forward in battery technology. This work discusses NMR methods for characterizing materials for use in battery application, with a special focus on relaxometry and diffusometry. Examples are provided of various recent investigations involving novel candidate electrolyte materials with different collaborators. Works discussed in this thesis include: the characterization of a new disruptive solid polymer electrolyte technology, investigations of the dynamics of super …

Instrumentation For Cryogenic Dynamic Nuclear Polarization And Electron Decoupling In Rotating Solids, Faith Joellen Scott

Arts & Sciences Electronic Theses and Dissertations

Dynamic nuclear polarization (DNP) increases the sensitivity of nuclear magnetic resonance (NMR) using the higher polarization of electron radical spins compared to nuclear spins. The addition of electron radicals for DNP to the sample can cause hyperfine broadening, which decreases the resolution of the NMR resonances due to hyperfine interactions between electron and nuclear spins. Electron decoupling has been shown to attenuate the effects of hyperfine coupling in rotating solids. Magic angle spinning (MAS) DNP with electron decoupling requires a high electron Rabi frequency provided by a high-power microwave source such as a frequency-agile gyrotron. This dissertation describes the development …

Spin Alignment Generated In Inelastic Nuclear Reactions, Daniel Hoff

Arts & Sciences Electronic Theses and Dissertations

The spin alignment of inelastically excited 7Li projectiles, when the target remains in its ground state, was determined through angular-correlation measurements between the breakup fragments of 7Li_ (_ + t). It was found that 7Li_ is largely aligned along the beam axis (longitudinal) in this type of inelastic reaction, regardless of the target. This longitudinal alignment is well described by DWBA calculations, which can be explained by an angular-momentum-excitation-energy mismatch condition. These calculations also explain the longitudinal spin alignment of excited nuclei in several other systems, showing the phenomenon is more general. The experiment involving 7Li was performed at the …

Structure And Thermodynamics Of Polyglutamine Peptides And Amyloid Fibrils Via Metadynamics And Molecular Dynamics Simulations, Riley Workman

Electronic Theses and Dissertations

Aggregation of polyglutamine (polyQ)-rich polypeptides in neurons is a marker for nine neurodegenerative diseases. The molecular process responsible for the formation of polyQ fibrils is not well understood and represents a growing area of study. To enable development of treatments that could interfere with aggregation of polyQ peptides, it is crucial to understand the molecular mechanisms by which polyQ peptides aggregate into fibrils. Many experimental techniques have been employed to probe polyQ aggregation, however, observations from these studies have not lead to a unified understanding of the properties of these systems, instead yielding competing, fragmented theories of polyQ aggregation. This …

A System For Conducting Laser-Induced Fluorescence Measurements On Gas Mixtures Exposed To Alpha Radiation, Patrick Ables

Master's Theses

This paper documents modifications to an existing vacuum system to allow laser-induced fluorescence spectroscopy measurements within simulated atmospheres under a variety of conditions. This added capability will expand the laboratory’s ability to experimentally validate a computational model that calculates the effects of radiation within the atmosphere. The computational model could reveal radiation-induced chemical products that can be used to develop an alternative detection method that can be implemented from a safe distance. The selection of molecules for experimental validation has been limited to those which can be detected utilizing cavity ringdown spectroscopy. The current model indicates nitric oxide and ozone …

Crystallographic Exploration Of Fundamental Technetium Species At Nonambient Conditions, Daniel S. Mast

UNLV Theses, Dissertations, Professional Papers, and Capstones

The study of mater under extreme conditions has yielded fascinating insight into the physical and chemical nature of materials that under more modest conditions are considered mundane but have quite unusual properties when under pressure. Examples of this are the lightest of elements found in the first two rows and in the heaviest elements of the lanthanide and actinide series. Pure elements, though the simplest possible chemical systems, have proven to be among the most complex and interesting. Technetium metal is a simple HCP transition metal that, due to its half-filled d-shell, has a rich chemistry and an important place …

Effects Of High Pressure On Photochemical Reactivity Of Organic Molecular Materials Probed By Vibrational Spectroscopy, Jiwen Guan

Electronic Thesis and Dissertation Repository

Chemical transformations of molecular materials induced by high pressure and light radiation exhibit novel and intriguing aspects that have attracted much attention in recent years. Particularly, under the two stimuli, entire transformations of molecular species can be realized in condensed phases without employing additional chemical constraints, e.g., the need of solvents, catalysts or radical initiators. This new synthetic approach in chemistry therefore satisfies increasing need for production methods with reduced environmental impacts. Motivated by these promises, my Ph. D thesis focuses on this state-of-the-art branch of high-pressure photochemistry. Specifically, high pressure is employed to create the necessary reaction conditions to …

Combined Spectroscopic And Scanning Probe Studies Of Electronic Interactions In Nanostructured 1d And 2d Semiconductors, Peijian Wang

Doctoral Dissertations

This dissertation includes the exploration about the following research questions: 1. What is the correlation between the work function and ground state interactions in organic semiconductor assemblies? 2. How do non-covalent chemical doping tune the work function in MoS₂? 3. Are there surface charges in the Aluminum doped ZnO nanocrystals (AZO) and what's the evolution of the surface charges and polarizabilities from undoped AZO to doped AZO? 4. How is the homogeneity like during doping in the organic thermoelectric materials? The techniques we employed in the research is the spatially registered Kelvin Probe Force Microscopy and Photoluminescence spectroscopy …

Accelerated Broadband Spectra And Attosecond Charge Migration Simulations Using Real-Time Time-Dependent Density Functional Theory, Adam S. Bruner

LSU Doctoral Dissertations

In this dissertation, the calculations of light-matter interactions offer insight into the structure and dynamical response of electrons in molecular systems. Such information is useful for characterizing molecules, electronic structure, photochemistry, photomaterials, and a host of other applications. In the first part of this work, simulations of broadband absorption spectra are accelerated by the use of Pad´e approximanants of Fourier Transforms and dipole decomposition. Electronic absorption spectra from valence and core levels are obtained using time-dependent methods and compared to results from established perturbative techniques. In addition, core level absorption spectra are calculated for a nickel porphyrin and shown to …

Surface Reaction And Diffusion Kinetics In Semiconducting Metal Oxide Film Gas Sensors, Aravind Reghu

Electronic Theses and Dissertations

Chemiresistive metal oxide gas sensors based on materials such as SnO₂, ZnO, and TiO₂, have been investigated extensively by many researchers for a wide range of applications. The band bending model, based on the surface chemistry of highly reactive ionosorbed species (O₂^- or O^-) and the semiconducting material properties of SnO₂, TiO₂ and ZnO, adequately predicts the dependence of the change in sensor conductivity (Δσ) as a function of target gas pressure and temperature. However, the band bending model is not applicable to gas sensors based on reducible oxides …

Compact Sensing Platforms Based On Localized Surface Plasmon Resonance, Zhutian Ding

Electronic Thesis and Dissertation Repository

The development of plasmonic sensors mainly focuses on the improvement of their sensitivities that are approaching the theoretical limit. This work aims to propose, fabricate and characterize compact sensing platforms that are highly adaptable and easy to be miniaturized, without compromising their sensitivities. A plasmonic sensing system that allows the excitation of localized surface plasmon resonance (LSPR) by individual waveguide modes is presented conceptually and experimentally. Another compact sensing platform is proposed based on the ensemble hypothesis developed in this thesis.

Characterization Of Polymers Containing Ferrocene And Imidazole With Density Functional Theory, Eric Mullins

Electronic Theses & Dissertations

Electrochemical and UV-Vis studies on these polymers in the presence of aqueous solutions containing metal ions have revealed significant modifications in the electrochemical properties and absorption spectra. These modifications in electrochemical properties could be attributed to the ability of the imidazole to coordinate with metal ions, increasing its electron deficiency and enhancing oxidization of the nearby ferrocene moiety if it is in close proximity with imidazole. However, the mechanism of interaction between the imidazole and metal ions, as well as the equilibrium geometry of the resulting polymer-metal ion complex is unknown.

In this thesis, density functional theory (DFT) was used …

Nadph-Cytochrome P450 Oxidoreductase: Extraction Of The Full-Length Protein And Methyl-Trosy Nmr Of The Soluble Mutants, Sara Ali Jamal Arafeh

Master's Theses (2009 -)

NADPH-cytochrome p450 oxidoreductase (CYPOR) is a membrane-bound protein in living cells. CYPOR delivers electrons to cytochrome p450 proteins (CYPs) to catalyze metabolism of drugs and synthesis of steroids. Extraction and solubilization of CYPOR from the membrane is typically done with the TritonX-100 detergent. The amount of the solubilized protein by this detergent, however, remains relatively low to structurally analyze CYPOR with NMR spectroscopy. The goal of the first project in this thesis was to optimize the amount of the extracted CYPOR from the E. coli membrane using various detergents and additives. To this aim, non-ionic detergents with variable hydrophobicity (TritonX-100, …

Functionalized Nanoporous Carbon Scaffolds For Hydrogen Storage Applications, Christopher Carr

Dissertations

Recent efforts have demonstrated confinement in porous scaffolds at the nanoscale can alter the hydrogen sorption properties of metal hydrides, though not to an extent feasible for use in onboard hydrogen storage applications, proposing the need for a method allowing further modifications. The work presented here explores how the functionalization of nanoporous carbon scaffold surfaces with heteroatoms can modify the hydrogen sorption properties of confined metal hydrides in relation to non-functionalized scaffolds (FS). Investigations of nanoconfined LiBH₄and NaAlH₄indicate functionalizing the carbon scaffold surface with nitrogen can shift the activation energy of hydrogen desorption in excess of …

Improving Fallout Characterization By Using Multivariate Techniques To Determine Composition, Christopher R. Pitkins

Theses and Dissertations

Multivariate statistical techniques have been applied in order to un-mix nuclear fallout debris chemical data. This information is critical to characterization of fallout particle formation following a nuclear detonation. Understanding the correlation between environmental precursors and actinide concentrations in post-detonation nuclear fallout material aids in understanding the physical and chemical processes that alter nuclear device signatures in the fireball. This research examines 123 nuclear fallout samples from a historical nuclear test. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) are used to collect chemical compositions of the fallout samples. Principal component analysis (PCA) is applied in order to examine …

Investigation Of Novel Electrolytes For Use In Lithium-Ion Batteries And Direct Methanol Fuel Cells, Kartik Pilar

Dissertations, Theses, and Capstone Projects

Energy storage and conversion plays a critical role in the efficient use of available energy and is crucial for the utilization of renewable energy sources. To achieve maximum efficiency of renewable energy sources, improvements to energy storage materials must be developed. In this work, novel electrolytes for secondary batteries and fuel cells have been studied using nuclear magnetic resonance and high pressure x-ray scattering techniques to form a better understanding of dynamic and structural properties of these materials. Ionic liquids have been studied due to their potential as a safer alternative to organic solvent-based electrolytes in lithium-ion batteries and composite …

Tunable Surface Interactions In Adsorbing Polymer Solutions, Sorour Hosseini

Open Access Theses & Dissertations

A simple formalism is suggested, to calculate the most likely configuration of a finite polymer, between two surfaces on which the monomers can adsorb. Grafted polymers typically enhance the stability of colloidal dispersions, via the long ranged steric repulsion due to the overlap of their polymer brushes, which can be thicker that the typical range of the DLVO interactions. However, if the polymers are adsorbing on the colloidal surfaces, there is the possibility of bridge formation between particles and therefore long-range attractions are induced (a procedure commonly used for the flocculation of colloidal suspensions). The two effects are competing and …

Block-Copolymer Assisted Fabrication Of Anisotropic Plasmonic Nanostructures, Calbi J. Gunder

MSU Graduate Theses

The anisotropic nanostructures of noble metals are of great interest for plasmonic applications due to the possibility of tuning the localized surface plasmon resonance (LSPR) across the UV-VIS-NIR without sacrificing the linewidth as well as to achieve larger local field enhancement. Here, we report a simple and promising fabrication method of anisotropic gold nanostructures film using polystyrene-b-2vinylpyridine (PS-b-P2VP) block copolymers (BCP) as a template. In this approach, PS-b-P2VP spherical micelles were first synthesized as a template followed by selective deposition of Au precursor inside P2VP core of the micelles using ethanol solution of Au salt. Subsequently, heat treatment of the …

Plasmon-Enhanced Optical Sensing By Engineering Metallic Nanostructures, Peng Zheng

Graduate Theses, Dissertations, and Problem Reports

The world’s booming population projected to reach 10 billion by 2050 causes enormous stresses on environmental safety, food supply, and healthcare, which in return threatens human civilizations. One of the most promising solutions lies at innovating point-of-care (POC) sensing technologies to conduct detection of environmental hazards, monitoring of food safety, and early diagnosis of diseases in a timely and accurate manner. The discovery of surface-enhanced spectroscopy in the 1970s has significantly stimulated research on light-matter interaction which gives rise to enhanced optical phenomena such as surface-enhanced Raman scattering (SERS), plasmon-enhanced fluorescence (PEF), and particularly, they have found enormous applications in …