Chemistry Commons^™

Synthesis And Properties Of Novel Macrocycles And Related Chromophoric Benzenoid Compounds, Jorge O. Escobedo Cordova

LSU Doctoral Dissertations

The synthesis and properties of some macrocyclic compounds of interest are presented. Resorcinarenes with functionalized conjugated rigid rods made of oligo-p-phenylenes would lead to an entirely new class of functional, soluble, well-defined architectures impacting a variety of multidisciplinary research efforts. The general synthetic design described in this document could be readly extrapolated to include other electronic systems such as heteroaromatics and polyenes. An extensive collaborative study of chromophore formation in resorcinarene solutions is also described here. The study reveals that upon oxidation, the reversible conversion to acyclic precursors occur first, and then these precursors undergo oxidation to quinoid-type compounds (xanthenes). …

Peroxynitrite-Mediated Oxidations: Nitration And Nitrosation, Rachel Bolzan

LSU Doctoral Dissertations

Using a direct ultraviolet second-derivative spectroscopy method, three peroxynitrite preparative methods were investigated for the nitrite and nitrate present either as impurities or produced during peroxynitrite decomposition: (I) ozonation of azide, reaction of hydrogen peroxide with (II) isoamyl nitrite and (III) nitrous acid. The oxidation of morpholine by peroxynitrite in the presence and absence of added carbonate gives N-nitromorpholine and N-nitrosomorpholine. Nitration and nitrosation of morpholine are catalyzed by low levels of CO₂; however, excess CO₂ dramatically reduces the yields of nitrosation but not nitration, and the combined yields of the products are about the same under …

Electronic And Structural Properties Of Rare Gas Cation Clusters, Jose Alejandro Gascon

LSU Doctoral Dissertations

We study structure and ground and excited state properties of rare gas cation clusters, Rg⁺_N, for N=3-60. The main goal is to understand how the positive charge is delocalized over the cluster and the relationship between cluster geometry and delocalization. He⁺_N, Ar⁺_N, and Xe⁺_N are selected as representatives of the rare gas elements. We perform Monte Carlo simulations to obtain finite temperature properties of the energy spectrum. The Hamiltonian of the system is based on a semi-empirical model whose parameters are obtained through the fitting of experimental and calculated …

Analysis Of Inorganic Materials Using Advanced Nmr And Nqr Techniques, Anthony Adrian Mrse

LSU Doctoral Dissertations

Several advanced solid-state nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) techniques have been applied to inorganic materials of commercial interest. The specific techniques applied to each system were chosen to solve specific obstacles which impeded the flow of industrial science.

First, the dispersion of brominated flame retardants in polymers is monitored using pulsed ⁸¹Br NQR (nuclear quadrupole resonance) techniques. The NQR spectrometer consists of a homemade NMR console and an automatically tuned loop-gap resonator probe. The two factors which affect the ⁸¹Br NQR transition frequencies of brominated aromatics are: electron-donating and withdrawing substituents on the ring …

Analysis Of Near-Infrared Dye-Labeled Sanger Sequencing Fragments With Gel Electrophoresis Using The Time-Resolved Flourescence Lifetime Indentification Methods, Suzanne Jeanel Lassiter

LSU Doctoral Dissertations

The research presented in this dissertation involves the identification of sequencing fragments with time-resolved methods. For this application, near-infrared heavy-atom tricarbocyanine dyes were developed in our laboratory, which can be excited with a single laser and emission collected using a single detection channel. The dyes have four spectroscopically unique, but relatively short lifetimes that can be altered by the intramolecular heavy-atom they contain. The work described here involves the optimization of dye-primer chemistry for preparing Sanger sequencing reactions for longer reads and the optimization of the separation matrix for capillary gel electrophoresis that produces favorable statistical analysis of the aforementioned …

The Synthesis Of Deuterated Arylamine Dna Adducts For Use In The Development Of An Isotope Dilution Lc/Ms/Ms Method, Philip Dmitri Olsen

LSU Doctoral Dissertations

Polycyclic aromatic amines (arylamines) are a class of chemical carcinogens that are prevalent in environmental and industrial settings. In order to study the mechanism of their toxicity a quantitative and qualitative detection method was developed to measure the C8-adenine adducts of benzidine and 2-aminofluorene in DNA samples. To do this a novel synthetic method using a palladium catalyst was developed to prepare authentic and deuterated arylamine adducts to serve as standards. These standards were then used to develop a high performance liquid chromatography, electrospray, tandem mass spectrometry, isotope dilution, detection method. To demonstrate the validity of this method two spike …