Chemistry Commons^™

Efficient Dehydrogenation Of Amines And Carbonyl Compounds Catalyzed By A Tetranuclear Ruthenium-Μ-Oxo-Μ-Hydroxo-Hydride Complex, Chae S. Yi, Do W. Lee

Chemistry Faculty Research and Publications

The tetranuclear ruthenium-μ-oxo-μ-hydroxo-hydride complex {[(PCy₃)(CO)RuH]₄(μ₄-O)(μ₃-OH)(μ₂-OH)} (1) was found to be a highly effective catalyst for the transfer dehydrogenation of amines and carbonyl compounds. For example, the initial turnover rate of the dehydrogenation of 2-methylindoline was measured to be 1.9 s⁻¹ with a TON of 7950 after 1 h at 200 °C. The extensive H/D scrambling patterns observed from the dehydrogenation reaction of indoline-N-d₁ and indoline-α-d₂ suggest a monohydride mechanistic pathway with the C−H bond activation rate-limiting step.

Derivatization Of Porphyrins For Dna And Metal Ion Binding, Especially By Employing Secondary Sulfonamide Links, Janet Manono

LSU Doctoral Dissertations

Porphyrins are of exceptional importance in nature, science and technology: For instance, as ligands for metals in supramolecular synthesis, as photosenstizers in photodynamic therapy (PDT), and as building blocks for electronic devices. In addition to their application in cancer therapy, porphyrin species also exhibit antiviral activity. New meso-tetraarylporphyrins (TArP, Ar = -C₆H₄-) of the general formula, T(R¹R²NSO₂Ar)P, with R¹ = N-py-n-CH₂ (n = 2, 3 or 4) or SO₃^- and R² = H or CH₃ were synthesized. These groups were linked to the …

Capillary Electrophoretic Separations Of Enzyme Inhibitors With Activity-Based Detection, Xiaoyan Yan

LSU Master's Theses

A technique for separating and detecting enzyme inhibitors was developed using capillary electrophoresis with an enzyme microreactor. The on-column enzyme microreactor was constructed using one or two NdFeB magnets in two configurations to immobilize alkaline phosphatase-coated superparamagnetic beads with diameters of 2.8 µm inside a capillary before the detection window. Enzyme inhibition assays were performed by injecting a plug of inhibitor into a capillary filled with an alkaline phosphatase substrate, AttoPhos. Product generated in the enzyme microreactor was detected by laser-induced fluorescence. Inhibitor zones electrophoresed through the capillary, passed through the enzyme microreactor, and were observed as negative peaks due …

Polymer-Based Microfluidic Devices For High Throughput Single Molecule Detection: Applications In Biological And Drug Discovery, Paul Ichide Okagbare

LSU Doctoral Dissertations

The realization of high throughput sample processing has become a primary ambition in many research applications with an example being high throughput screening (HTS), which represents the first step in the drug discovery pipeline. Microfluidics is a viable platform for parallel processing of biochemical reactions to increase data production rates due to its ability to generate fluidic networks with a high number of processors over small footprints suitable for optical imaging. Single-molecule detection (SMD) is another technology which has emerged to facilitate the realization of high throughput data processing afforded by its ability to eliminate sample processing steps and generate …

Patterning High Surface Area Silica With Lysozyme: Adsorption Kinetics, Fluorescence Quenching, And Protein Readsorption Studies To Evaluate The Templated Surface, Rachel M. Greer, Brittni A. Scruggs, R Alan May, Bert D. Chandler

Chemistry Faculty Research

A method was developed for using an inexpensive and widely available protein, hen egg white lysozyme, as a patterning agent for commercial high surface area silicas. The basic patterning methodology involved spontaneous adsorption of the protein from aqueous solution, alkylation of the uncovered surface with an alkylsiloxane, and protein desorption in a slightly alkaline solution of morpholine. Adsorption kinetic studies using Bradford assays assisted in determining protein deposition conditions. These studies were generally consistent with results on more planar silica surfaces and indicated that the protein quickly and strongly adsorbs along its long axis at low surface coverages. A modified …

Characterization And Transitions Of Asphalt Cement Composite Materials, Brent Harper Sellers

LSU Master's Theses

Blends of a PG 64-22 asphalt with a range of load levels (0.2 — 20 wt %) of Sasobit® wax and a single loading of 2 wt % Elvaloy AM® were prepared and characterized. Sasobit® wax is a high molecular weight paraffinic wax produced commercially through the Fischer-Tropsch process. Elvaloy AM® is a reactive elastic terpolymer, comprised of ethylene, butyl acrylate and glycidyl methacrylate monomeric units. The blends were analyzed by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), x-ray diffraction, epifluorescence microscopy, scanning laser confocal microscopy, and dynamic shear rheology. Sasobit (1 wt %) composite material showed little difference …

Studies On The Effect Of Natural Organic Matter And Hydration On The Sorption And Desorption Of Trifluorinated Pesticides, Charisma Vinarao Lattao

LSU Doctoral Dissertations

This work was done in order to deepen our molecular level understanding of how soil organic matter (SOM) is assembled in a whole soil and to provide further insight on the effect of SOM assembly on the uptake and release of hydrophobic organic compounds. Various techniques, including ultraviolet absorbance, fluorescence, and total carbon analysis, demonstrate that hydration/solvation of SOM is kinetically controlled. Initial wetting of a soil releases the hydrophobic moieties that are located at the outer surface of SOM, and longer wetting times exfoliate more hydrophobic quinone type moieties that are present in the middle layer, which in turn …

Scanning Probe Microscopy Investigations Of (1) Arrays Of Cysteine-Coated Cds Nanoparticles And (2) Structures Formed During The Early Stages Of The Corrosion Of Copper Surfaces, Brian Robert Lewandowski

LSU Doctoral Dissertations

Scanning probe microscopy (SPM) characterizations are becoming more prevalent for surface investigations due to their capabilities for obtaining structural information and physical measurements. New capabilities of SPM for studying and controlling nanoscale processes are emerging as valuable assets in research. A fundamental understanding of the interactions of surface reactions provides essential information for developing workable applications for nanotechnology. Two applications of SPM are discussed in this dissertation. The first investigation uses atomic force microscopy (AFM) for the characterization of nanostructures produced with a newly developed lithographic technique called “two-particle” lithography. This new technique is based on particle lithography for the …

Atom-Based Computer Simulation Studies Of Gas-To-Liquid Nucleation In Atmospherically Relevant Systems: Clarifying Discrepancies And Elucidating Mechanisms, Ricky Bendanillo Nellas

LSU Doctoral Dissertations

For over a century, nucleation for all systems was thought simplistically to be a process that advances through the formation of critical clusters with a well-defined composition. Our results show intriguing nucleation mechanisms that challenge the aforementioned notion. We employed the simple TraPPE-UA (transferable potential for phase equilibria – united atom) force field and the AVUS-HR approach (a combination of aggregation-volume-bias Monte Carlo, umbrella sampling, and histogram reweighting), to investigate the homogeneous vapor-to-liquid nucleation of various nucleating systems. We found out that these systems could nucleate through a variety of unique non-ideal mechanisms. Alongside existing experimental investigations, this dissertation presents …

Iron Mediated Pecipitation Of Phenol: Protein Aggregates From Sugar Cane Juice, Lee R. Madsen Ii

LSU Doctoral Dissertations

The Louisiana cane sugar industry is moving toward a vertically integrated arrangement where raw sugar producers will have an interest in refining. In the sugar refining process, raw sugar is affined to remove ~50 % of the color. The new refinery that will be built in Louisiana, however, will not include affining stations. To reduce costs of refining, either affining stations will need to be installed at each mill or new technologies that provide equivalent color reduction (~50% or ~750 IU) need to be implemented. As part of this dissertation a new technology for color reduction at raw sugar mills …

Fabrication Of Nanostructured Surfaces With Well-Defined Chemistry Using Particle Lithography, Jie-Ren Li

LSU Doctoral Dissertations

Natural self-assembly processes provide nanofabrication capabilities for designing surfaces with nanoscale control of surface chemistry and relative orientation of the nanomaterials on the surfaces. Particle lithography was used to produce periodic arrays of protein nanostructures. Monodisperse mesoparticles can be applied to rapidly prepare millions of uniform protein nanostructures on flat surfaces using the conventional benchtop chemistry steps of mixing, centrifuging, evaporation and drying. Nanopatterns of bovine serum albumin and staphylococcal protein A were produced with particle lithography. The immobilized proteins remain attached to the surface and form nanopatterns over micron areas corresponding to the thickness of a single layer of …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Structural Studies Of Biopolymers Using Computer Simulations, Optical And Magnetic Spectroscopy, Subhasish Chatterjee

Dissertations, Theses, and Capstone Projects

Biopolymers are essential components of numerous natural and synthetic macromolecular assemblies. In the present study, the structural properties of biopolymers ranging from fungal melanins to synthetic nucleic acids were investigated using spectroscopic methods and theoretical modeling. (1) Computational modeling and molecular dynamics simulations were used to study the structural properties of a short single-stranded (ss) DNA. The dependence of the conformational stability and flexibility of the ssDNA on the thermodynamic conditions of the system was demonstrated. (2) Time-resolved fluorescence spectroscopy involving an organic donor-quencher pair was utilized to study the conformational properties of Y-shaped DNA. Results highlighted the different distances …