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Full-Text Articles in Chemistry
Infrared Investigation Of Lithium Ion Electrolytes: Characterization Of Structure And Dynamics Via Linear And Nonlinear Spectroscopy, Jeramie Christopher Rushing
Infrared Investigation Of Lithium Ion Electrolytes: Characterization Of Structure And Dynamics Via Linear And Nonlinear Spectroscopy, Jeramie Christopher Rushing
LSU Doctoral Dissertations
Lithium ion batteries are widely employed in energy storage, but the connection between the molecular interactions in their electrolytes and the macroscopic properties remains elusive. Across three vastly different electrolytes, speciation and dynamics were studied via linear and nonlinear infrared spectroscopy to shed light on this relationship. The impact of mixed solvation on ionic speciation was studied from the perspective of the anion, which revealed a significant energetic favorability for the formation of contact ion pairs in linear carbonate solvents over cyclic carbonates. Infrared spectroscopy and density functional theory calculations described a complete inversion of the speciation due to solvent …
Second Harmonic Generation Spectroscopy And Microscopy Of Liposomes, Nanoparticles, And Cells, Prakash Hamal
Second Harmonic Generation Spectroscopy And Microscopy Of Liposomes, Nanoparticles, And Cells, Prakash Hamal
LSU Doctoral Dissertations
Second harmonic generation (SHG) is used to investigate the factors that impact nanoparticle-based drug-delivery applications. In the first study, molecular adsorption and transport kinetics of a positively-charged dye, malachite green isothiocyanate (MGITC), is characterized at the surface of different colloidal liposomes in water using SHG spectroscopy. The molecular interactions of MGITC is compared to our previous investigations with malachite green (MG). In comparison to MG, MGITC demonstrates stronger adsorption and faster transport through lipid membranes. Correspondingly, the SHG experimental results are in excellent agreement with the molecular dynamics (MD) simulations results. A key finding illustrates the importance of functional groups, …
Nanoparticle-Based Drug-Delivery Systems Studied By Second Harmonic Generation, Raju Ram Kumal
Nanoparticle-Based Drug-Delivery Systems Studied By Second Harmonic Generation, Raju Ram Kumal
LSU Doctoral Dissertations
Second harmonic generation (SHG) is used to study different types of colloidal nanoparticle drug-delivery systems. The surface charge density, electrostatic surface potentials, and ion adsorptions of 50 nm colloidal gold nanoparticle samples coated with mercaptosuccinic acid are determined using SHG measurements under varying NaCl and MgCl2 concentrations in water. Numerical solutions to the spherical Poisson-Boltzmann equation are fit to the SHG results to account for the nanoparticle surface curvature and ion adsorption to the Stern layer interface, showing excellent agreement with electrophoretic mobility measurements. In another study, nanoparticles of gold, silver and polystyrene are functionalized with microRNA using a …
Photoelectrons And Recombining Electrons In Atomic And Molecular Systems, Kristen D'Ann Fulfer
Photoelectrons And Recombining Electrons In Atomic And Molecular Systems, Kristen D'Ann Fulfer
LSU Doctoral Dissertations
This work in this dissertation explores how photoelectrons enter and exit atoms and molecules. The electron rescattering events which may occur during photoionization or photorecombination processes play a dominant role in the understanding of how photoelectrons enter and exit molecules, which is intrinsically linked to how chemical reactions occur. Chapters 3-4 of this dissertation present evidence of vibrational mode specific breakdown of the Franck-Condon Principle in the photoionization of low symmetry molecules, acrolein and the singly halogenated thiophenes, due to resonant and non-resonant electron rescattering dynamics. In Chapters 5-6, the disentanglement of the valence electronic structure, as well as evidence …
Investigating The Photorecombination Dynamics In Molecular High-Harmonic Spectra, Benjamin Parker Wilson
Investigating The Photorecombination Dynamics In Molecular High-Harmonic Spectra, Benjamin Parker Wilson
LSU Doctoral Dissertations
The work presented in this dissertation will relate the photorecombination dynamics to photoionization dynamics in SF6 utilizing the self-probing mechanism, high harmonic generation (HHG). This work specifically aims to establish parameters for which the comparison is applicable and the macroscopic complications inherent in HHG do not interfere with the extraction of dynamic information. The first part of this work established the macroscopic experimental apparatus necessary for consistent spectroscopic observation. It is shown that using a gas jet that is an order of magnitude shorter than the Rayleigh length of the driving laser results in more consistent harmonic spatial profiles and …
Gumbos And Nanogumbos: Applications As Photosensitizers In Dye-Sensitized Solar Cells, Atiya Nicole Jordan
Gumbos And Nanogumbos: Applications As Photosensitizers In Dye-Sensitized Solar Cells, Atiya Nicole Jordan
LSU Doctoral Dissertations
Renewable energy is a major concern due to increased world energy consumption. In particular, solar energy is a type of renewable energy source that uses devices known as solar cells to convert sunlight to electricity. Specifically, devices referred to as dye-sensitized solar cells (DSSCs) employ dyes to absorb solar energy. Dyes derived from ruthenium complexes have been typically used in DSSCs. Unfortunately, several disadvantages are associated with current ruthenium complex photosensitizers, which can be attributed to limited supply and expense of metals, as well as reduced absorption in the near-infrared region of the electromagnetic spectrum. Accordingly, this dissertation is a …
Novel Nonresonant And Resonant Mechanisms Leading To The Breakdown Of The Franck-Condon Approximation In Photoionization, David Adam Hardy
Novel Nonresonant And Resonant Mechanisms Leading To The Breakdown Of The Franck-Condon Approximation In Photoionization, David Adam Hardy
LSU Doctoral Dissertations
This thesis attempts to answer the question of how electrons interact with a molecular framework prior to and during emission through photoionization. These studies interrogate several behaviors of allowed and forbidden photoelectron transitions such as shape resonances, non-resonant intrachannel vibronic coupling as a result of Cooper minima, and chemically-induced nonresonant coupling, all of which provide new insights into correlations between the electronic and molecular degrees of freedom. Research presented in this thesis utilizes high-resolution photoelectron spectroscopy, and undulator-based synchrotron radiation at the Advanced Light Source, a synchrotron radiation source in Berkeley, California. Data are collected from near threshold to several …
Studies On A Dirhodium Tetraphosphine Hydroformylation Catalyst, Darina Polakova
Studies On A Dirhodium Tetraphosphine Hydroformylation Catalyst, Darina Polakova
LSU Doctoral Dissertations
The dirhodium tetraphosphine catalyst [Rh2(nbd)2(rac-et,ph-P4)](BF4)2 was investigated in acetone and water/acetone in order to explain better hydroformylation results in the latter solvent. In-situ NMR spectroscopy showed slower degradation in water/acetone. Less tendency to form penta/hexacarbonyl complexes in water/acetone was shown by 31P{1H} NMR and FT-IR. A pH decrease and hydroformylation studies in presence of a base indicated formation of a monocationic monohydride species. A new reaction mechanism was suggested that takes into account the observed differences from the acetone solvent system. The presence of water enabled production of hydride species when the dirhodium catalyst was exposed to CO gas. We …
Synthesis, Characterization, And Application Of Water-Soluble Chiral Calix[4]Arene Derivatives In Spectroscopy And Capillary Electrokinetic Chromatography, Kim Hamilton
LSU Doctoral Dissertations
This dissertation is an account of the synthesis, characterization, and application of novel water-soluble chiral calixarenes in spectroscopy and capillary electrophoresis. It is divided into four sections. The first part describes the synthesis and nuclear magnetic resonance (NMR) characterization of four p-t-butylcalix[4]arenes bearing L-amino acid moieties on their lower rims (CX4-AA). The structure and conformation of the derivatives have been determined using one- and two-dimensional NMR techniques. Proton and carbon-13 spectra show that the derivatives are tetra-substituted and adopt a cone conformation. The preparation and characterization of silica-bonded calixarene stationary phases for capillary electrochromatography is also reported in Chapter 2. …