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Development Of Remote Hydroxylation Via Redox Catalysis And Mild Activation Of Thioglycosides For O-Glycosylation, Kristina Deveaux Nov 2017

Development Of Remote Hydroxylation Via Redox Catalysis And Mild Activation Of Thioglycosides For O-Glycosylation, Kristina Deveaux

LSU Doctoral Dissertations

The focus of this dissertation is the development of a C-H functionalization method using redox catalysis and the synthesis of saccharides using thioglycosides. Chapter 1 is a review of C-H functionalization and visible-light photoredox catalysis. Over the years there have been many significant contributions to the field of C-H functionalization. Select examples have been discussed and a foundation for the method developed in chapter 2 has been outlined. Chapter 2 discusses the development and optimization of a C-H functionalization method. This approach uses the Tzo directing group and Ir(ppy)3 to activate a remote C-H bond via 1,6- and …


Nanopatterns Of Zinc Phthalocyanines, Gold Nanoparticles, And Porphyrins Prepared Using Particle Lithography: Characterization Of Patterning Steps With Scanning Probe Microscopy, Ashley Marie Taylor Nov 2017

Nanopatterns Of Zinc Phthalocyanines, Gold Nanoparticles, And Porphyrins Prepared Using Particle Lithography: Characterization Of Patterning Steps With Scanning Probe Microscopy, Ashley Marie Taylor

LSU Doctoral Dissertations

The growth and self-assembly of molecules on surfaces can be directly visualized at the molecular level using studies which combine nanoscale lithography and high-resolution imaging. Nanopatterning provides a unique and practical approach for direct views of surface changes after the key chemical steps of nanopatterning, providing landmarks and baselines for measuring growth in vertical and lateral dimensions. Controlling the arrangement of materials on surfaces at the nanoscale can be achieved using particle lithography. Arrays of well-defined nanostructures can be prepared with reproducible geometries and arrangement. Results for the preparation of nanopatterns produced with particle lithography are presented using high resolution …


Coupled Plasmon/Molecule Dynamics Near Core-Shell Nanoparticles: Synthesis, Ultrafast Characterization, And Quantum/Classical Modeling, Holden Tyler Smith Nov 2017

Coupled Plasmon/Molecule Dynamics Near Core-Shell Nanoparticles: Synthesis, Ultrafast Characterization, And Quantum/Classical Modeling, Holden Tyler Smith

LSU Doctoral Dissertations

In this dissertation, the resonance coupling of chromaphoric dyes adsorbed on the surface of plasmonic nanoparticles (NPs) are investigated using a combined theoretical and experi- mental approach. Colloidal gold, gold-silver core-shell, silver-gold core-shell, and gold-silver- gold core-shell-shell NPs are considered. These NPs are thiolated with mercaptosuccinic acid, and malachite green dyes are adsorbed to the surface of the nanoparticle (NP) via elec- trostatic interactions. Second harmonic generation is used to determine the surface to the isotherm of the molecular dyes to the colloidal nanoparticle surface. Adsorption isotherms show that the SHG intensity increases as the concentration of dye increases, reaching …


Self-Assembly Mechanisms Of Organosilanes And Porphyrins Investigated With Scanning Probe Microscopy, Phillip Charles Chambers Ii Nov 2017

Self-Assembly Mechanisms Of Organosilanes And Porphyrins Investigated With Scanning Probe Microscopy, Phillip Charles Chambers Ii

LSU Doctoral Dissertations

This dissertation details the development of new fabrication strategies for the preparation of spatially selective surfaces by combining techniques of particle lithography and scanning probe microscopy (SPM). This combination of lithography and nanoscale surface characterization was applied to study the mechanisms of molecular level surface-assembly of organosilanes and porphyrin on surfaces of Si(111). Particle lithography was used to investigate the surface assembly of 4-chloromethylphenyltrichlorosilane (CMPS) within exposed sites of nanoholes in selected solvents and at selected temperatures to gain insight into the details of self-polymerization. Nanopillars of CMPS were generated under selected conditions of solvent and temperature and characterized with …


New Synthetic Reactions Towards Global Chlorination And Enamides Functionalization, Mirza Ardella Saputra Oct 2017

New Synthetic Reactions Towards Global Chlorination And Enamides Functionalization, Mirza Ardella Saputra

LSU Doctoral Dissertations

This dissertation focuses on two main projects, global chlorination and enamide functionalization, which both encompass in cationic intermediates. Inspired by the desires to find a new chlorination method, global chlorination project is emphasized in chapter one and chapter two, in which chapter one details various known chlorine-containing natural products, including alkyl chlorides and vinyl chlorides. This chapter also describes the previously known protocols to synthesize alkyl chlorides in the attempts of chlorosulfolipids total syntheses, as well as several known reactions to synthesize vinyl chlorides that are both important functional groups in organic synthesis. Chapter two depicts our novel synthetic reaction …


Hydroformylation And Aldehyde-Water Shift Catalysis By Dirhodium Tetraphosphine Complexes, Marshall Douglas Moulis Aug 2017

Hydroformylation And Aldehyde-Water Shift Catalysis By Dirhodium Tetraphosphine Complexes, Marshall Douglas Moulis

LSU Doctoral Dissertations

The use of a unique tetraphosphine ligand (et,ph-P4) allows for the chelating of two rhodium centers to perform bimetallic coopertivity in hydroformylation reactions to better the yields the linear aldehyde product. The proposed catalyst is [Rh2(μ-H)2(CO)4(rac-et,ph-P4)]2+ and has been studied by in situ FT-IR and NMR. When tested in a polar phasic acetone/water (30 % by vol.), the catalyst forms a monocationic system [Rh2(μ-H)2(CO)4(rac-et,ph-P4)]+ that has an initial TOF of 26 min-1, selectivity of 27:1 L:B, and low byproducts of …


Nanoparticle-Based Drug-Delivery Systems Studied By Second Harmonic Generation, Raju Ram Kumal Aug 2017

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 …


Synthesis Of Β-Methyl-L-Cysteine As A Model For A Β-Methyl-D-Cysteine Building Block For Incorporation Into Microbisporicins, Elora C. Doskey Apr 2017

Synthesis Of Β-Methyl-L-Cysteine As A Model For A Β-Methyl-D-Cysteine Building Block For Incorporation Into Microbisporicins, Elora C. Doskey

Honors Theses

No abstract provided.


Effect Of Metal Speciation In Fly Ash On Environmentally Persistent Free Radical Formation, Elisabeth Eileen Cook Jan 2017

Effect Of Metal Speciation In Fly Ash On Environmentally Persistent Free Radical Formation, Elisabeth Eileen Cook

LSU Doctoral Dissertations

Waste incineration and Superfund sites lead to the formation of pollutants harmful to both the environment and human health. Environmentally Persistent Free Radicals (EPFRs) are a class of newly discovered radical pollutants known to form on combustion by-products such as fly ash and particulate matter. EPFRs are rapidly gaining attention for their harmful effects on the environment and human health. Previous research has shown the formation of EPFRs through surface-mediated reactions with transition metal-oxides on particulates. The work presented in this dissertation explores the relationship between fly ash composition and EPFR formation. Fly ash production occurs from combustion systems, namely …


Application Of Grating-Based Interferometry To Additive Manufacturing, Lithium-Ion Batteries, And Crystals, Adam Joseph Brooks Jan 2017

Application Of Grating-Based Interferometry To Additive Manufacturing, Lithium-Ion Batteries, And Crystals, Adam Joseph Brooks

LSU Doctoral Dissertations

X-ray and neutron imaging are convenient ways to non-destructively observe novel materials. X-rays provide advantages of low cost and high brilliance while neutrons show bulk and isotopic sensitivity. Imaging provides a way for observing chemical and physical properties of materials without the need for destruction. The way of the imaging future is utilizing imaging with grating-based interferometry. In comparison to traditional radiography and tomography, by using absorption and phase gratings in the beam path, the absorption, phase, and scattering of a sample can be detected. In essence, three image datasets can be obtained in one experiment, saving substantially on costs …


Nanoscale Studies Of Proteins And Thin Films Using Scanning Probe Microscopy, Zachary Lane Highland Jan 2017

Nanoscale Studies Of Proteins And Thin Films Using Scanning Probe Microscopy, Zachary Lane Highland

LSU Doctoral Dissertations

Nanostructures of organosilanes, thin metal films, and protein nanopatterns were prepared and analyzed with atomic force microscopy (AFM). Organosilanes with designed functional groups were used to selectively pattern green fluorescent protein at the nanoscale using protocols developed with particle lithography. Mesospheres are deposited onto a substrate to produce a surface mask. Organosilanes are deposited to form a matrix film surrounding nanopores for depositing proteins. The nanopatterns were characterized using AFM, after steps of particle lithography for directly visualizing surface changes. Studies with AFM also provide a compelling tool for teaching undergraduates to introduce concepts of nanoscience. An undergraduate laboratory was …


Chemical Synthesis: New Methods For O-Glycosylation And The Preparation Of Organic Thin Films, Rashanique Deondria Quarels Jan 2017

Chemical Synthesis: New Methods For O-Glycosylation And The Preparation Of Organic Thin Films, Rashanique Deondria Quarels

LSU Doctoral Dissertations

This dissertation focuses on the diverse use of chemical synthesis. Herein, I will discuss the use of synthetic organic chemistry for the modification surfaces and the synthesis of small molecules. Chapter One is an introduction to the realm of surface chemistry. I have highlighted some key methods for surface modification. Additionally, methods to characterize the as-formed thin films are also outlined. In Chapter Two, I discuss the use of visible-light photoredox catalysis in the nanoscale lithography of Au(111) surfaces. Blue LED irradiation of solutions of NBDT in the presence of Ru(bpy)32+ results in the formation of p-nitrophenyl radicals that graft …


Design, Synthesis, And Evaluation Of Innovative Bodipy-Peptidic Conjugates For Biological Application, Tyrslai Menyaee Williams Jan 2017

Design, Synthesis, And Evaluation Of Innovative Bodipy-Peptidic Conjugates For Biological Application, Tyrslai Menyaee Williams

LSU Doctoral Dissertations

Abstract Chapter 1 provides a brief introduction to colorectal cancer (CRC), methods of detection, photodynamic therapy (PDT), and EGFR as an attractive targeting strategy for imaging CRC. Chapter 2 details the synthesis of ten peptide sequences for targeting EGFR receptors at the site of CRC, as a collaborative work with Dr. Seetharama Jois. This chapter also investigates the efficacy of these peptides for EGFR. Chapter 3 offers the first synthetic strategy for developing BODIPY-peptide conjugates via amide linkages. All conjugates were optimized for the best reaction conditions and good yields were observed. Each conjugate was subjected to photophysical, SPR, and …


Design, Synthesis, Characterization And Evaluation Of Near Infrared Bodipy Dyes For Various Applications, Qianli Meng Jan 2017

Design, Synthesis, Characterization And Evaluation Of Near Infrared Bodipy Dyes For Various Applications, Qianli Meng

LSU Doctoral Dissertations

4,4-Difluoro-4-bora-3a,4a-diaza-5-indacene (BODIPY) have drawn a large number of research attention, for its numerous useful application in the fields of material and biology. Small modification of this well-known fluophore has been shown to optimize its photophysical and chemical properties. This work mainly focuses on functionalization of BODIPY cores with halogenated atoms, particularly iodine, and their subsequent post-functionalization reactions, mainly cross-coupling reaction and substitutions, for various further applications. Chapter 1 of this dissertation gives a general overview of BODIPYs including their synthetic strategies, post-functionalization, and how BODIPYs are utilized in many biological applications. Chapter 2 mainly focuses on the synthesis and characterization …


Improved Protein Characterizations Using Ionic Liquids: Page And Maldi-Ms, Punprabhashi Vidanapathirana Jan 2017

Improved Protein Characterizations Using Ionic Liquids: Page And Maldi-Ms, Punprabhashi Vidanapathirana

LSU Doctoral Dissertations

Protein separation by polyacrylamide gel electrophoresis (PAGE) and identification by matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) are primary tools of protein analysis. In these techniques, surfactants are used in protein sample preparation in order to enhance the protein solubility. Conventional surfactants have shown limitations in protein analysis due to the structural complexity of proteomes, resulting in low resolution. The research goal of this dissertation is to address some of these limitations by applying novel cationic ionic liquid surfactants (ILS), N-alkyl-4-methyl pyridinium bromide (CnPBr where n=4, 8, 11). The ILS would be suitable candidates to be used in PAGE protein …