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Xps Characterization Of Supported Iron/Ruthenium Carbon Monoxide Hydrogenation Catalyst Systems., Jeffry T. Donner

LSU Historical Dissertations and Theses

Literature in the field of catalysis is dominated by details of catalytic reactions, operating conditions, and product streams, with little regard for detailed physical characterization of the catalyst materials. It is now understood that knowledge of catalyst properties as a function of reaction properties may lead to the design of more active and/or selective catalysts. Thus, studies in the catalysis field are changing and the present investigation demonstrates the utility of an X-ray photelectron spectroscopic (XPS) characterization of supported iron, ruthenium, and iron-ruthenium bimetallic catalyst systems as a function of catalyst treatment(s). This physical and chemical information of the catalysts …

Statistical Mechanics Of Conformational Transitions In Biopolymers., Rachid Charbel Maroun

LSU Historical Dissertations and Theses

Recently extended theoretical methods and existent experimental methods have been employed for the determination of conformational-dependent properties of polymers of biological interest like synthetic polyamino acids, natural polypeptides and proteins. Calculation of theoretical properties, like for example average helical content and average helical length, as derived from the configuration partition function has been achieved by making use of the Rotational Isomeric State approximation through modifications and innovations of a nearest-neighbor interaction version of the Zimm-Bragg model of helix-coil transitions as presented in a matrix format suitable for use in an electronic computer. The scope of the theory allows for the …

New Sesquiterpene Lactones From The Genera Calea And Berlandiera (Asteraceae) And The Fragmentation Reactions Of 1,3-Dihydroxyeudesmanolide Derivatives., Ihl Young Lee

LSU Historical Dissertations and Theses

Chemical analysis of Calea ternifolia var. calyculata (syn. Calea hypoleuka, Calea salmaefolia, and Calea albida) yielded the known sesquiterpene lactone calein A (21) and the atripliciolide derivatives, 11,13-dyhydro-11(alpha),13-epoxyatripliciolide-8(beta)-O-angelate (51), 11,13-dihydro-11(alpha),13-epoxyatripliciolide-8(beta)-O-methacrylate (52), and 9(alpha)-hydroxy-11,13-dihydro-11(alpha),13-epoxyatripliciolide-8(beta)-angelate (54). In addition, three new germacranolides, 8(beta)-angeloyloxy-9(alpha)-{2-methylbutanoyloxy} ternifolin (32), 8(beta)-angeloyloxy-9-acetoxyternifolin (33) and five furanoheliangolides, 9(alpha)-acetoxyzexbrevin (36), 9(alpha)-hydroxyzexbrevin (37), 8(beta)-angeloyloxy-9(alpha)-hydroxycalyculatolide (38), 9(alpha)-hydroxy-11,13-dihydro-11(alpha),13-epoxyatripliciolide 8(beta)-O-methacrylate (55) and 15-hydroxy-11,13-dihydro-11(alpha),13-epoxyatripliciolide (56) were isolated. The structures of the new compounds were elucidated by NMR and mass spectral methods. Single crystal X-ray diffraction of the lactones 36 and 55 established their molecular structure. Calea ternifolia var. ternifolia (syn. Calea liebmanii) provided the new sesquiterpene …

The Syntheses Of The Crown Ethers Possessing 2,6-Pyridino Moieties., Hyo Won Lee

LSU Historical Dissertations and Theses

In an attempt to synthesize "Type 2" nicotinic acid crown ethers with a 3-carbinol appendage group, unexpected facile etherification was encountered during the cleavage of the tetrahydropyranyl (THP) group in acidic alcoholic media. The rationale for this reaction was provided by the examination of reactions with non-cyclic model compounds, and their THP derivatives in order to isolate any effects of the crown ether bridge. The 2,6-disubstituted dialkoxy groups were found to contribute to the stabilization of the carbonium ion derived from the protonation of the 3-pyridyl carbinols. Thus, nicotinic crown ether with a 3-carbinol group was prepared with the exclusion …

Structure Elucidation And Chemistry Of Sesquiterpene Lactones From The Subtribe Melampodiinae., Arcelio Jose Malcolm

LSU Historical Dissertations and Theses

The isolation and structure determination of seven new cis-1(10), cis-4-germacranolides, longicornin A-D, from Melampodium longicorne, 9-desacetoxymelcanthin F from Polymnia maculata, and 9-desacetoxymelcanthin A and 9-desacetylmelcanthin B from M. leucanthum is described. The structure, configuration and conformation of the new compounds were determined by chemical transformations, and spectral correlation using NMR, MS and CD. The single crystal X-ray diffraction of longicornin A represented the first crystal structure of a germacra-cis-1(10), cis-4-dien-trans-6,12-olide. Sodium borohydride reduction of 2(beta)-hydroxy-cis,cis-germacranolides formed rearrangement products under loss of the ester function at C-9 and double bond migration from 1(10) to the 9(10) position, via S(,N)2' reactions involving …

A Study Of Several Macrocyclic Beta-Ketoamines And Their Metal Chelates., Charles Louis Modenbach Iii

LSU Historical Dissertations and Theses

Two new series of macrocyclic (beta)-ketoamines and several of their metal chelates have been prepared and characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis. The two series of (beta)-ketoamines are of type: and. where n = 3,6,7, and 10. They were prepared by reaction of macrocyclic (beta)-diketones with ammonia or ethylenediamine. These compounds were found to exist predominantly in the ketoamine form. A survey was conducted to determine the metal chelation behavior of the macrocyclic (beta)-ketoamines and a few (beta)-ketoamines derived from acetylacetone. The metals and oxocations used in this study were Be(II), Mg(II), Al(III), …

Chemical Modifications Of Condensation Polymers, Chloromethylation And Quaternization., Shih-Jen Wu

LSU Historical Dissertations and Theses

Chloromethyl methyl ether, 6, generated in situ by reaction of dimethoxymethane with acetyl chloride, was employed to chloromethylate condensation polymers containing oxy-1,4-phenylene repeat units, i.e. poly(oxy-2,6-dimethyl-1,4-phenylene), 3, polyarylether sulfone, 4, and acetylated phenoxy resin, 10. To minimize concomitant crosslinking, the optium reaction ratios are 20:1:0.1 for reagent 6 to polymer to SnCl(,4) catalyst. One chloromethyl group per activated aromatic ring could be introduced: the corresponding concentration of active sites were 5.8, 3.5, and 4.6 meq/g for derivatives of 3, 4, and 10, respectively. All of the derivatives were characterized by NMR, DTA, and TGA techniques. A model segment of polyarylether …

Sensors Based On Immobilized Fluorogenic Reagents, Linda Anne Saari

Doctoral Dissertations

Sensors based on the fluorescence of immobilized fluorogenic reagents are prepared and their characteristics are defined. The fluorogenic reagent is chemically immobilized on a solid support and attached to the common end of a bifurcated fiber optic bundle. Fluorescence is excited through one arm of the fiber optic and observed through the other arm. The fluorogenic reagents fluoresceinamine, morin, calcein, and quinalizarin are immobilized on powdered cellulose via cyanuric chloride.

Consistent with previous studies of the pH dependence of fluorescein, the fluorescence from the immobilized fluoresceinamine sensor increases with pH. Immobilized fluoresceinamine serves as a viable pH sensor, but can …

The Determination Of Stability Constants And Complexing Capacities Of Natural Organic Matter For Copper (2+), Cobalt (2+) And Manganese (2+) By Fluorescence Quenching Titration, David K. Ryan

Doctoral Dissertations

The purpose of this study is to develop methodologies for the investigation of the metal ion binding properties of natural humic substances. Humic materials are prevalent in soil and water and their important metal ion detoxification and transport properties are the major justification for this work. The primary emphasis is the determination of the complexing capacity of a sample for a particular metal ion under fixed conditions.

The initial part of the investigation involves the application of chelating ion exchange to remove and quantify humic-chelated trace metal ions from water samples. Amine, dithiocarbamate and 8-hydroxyquinoline chelating agents immobilized on porous …

The Study And Characterization Of A New Procedure For Applying Carbide Coatings To Graphite Furnaces Used In Atomic Absorption Spectroscopy, Manuel Charles Almeida

Doctoral Dissertations

The object of this dissertation is the study and characterization of a new method for applying carbide coatings to graphite furnaces used in atomic absorption spectroscopy. The proposed method consists of impregnating graphite furnaces, under reduced pressure, with a liquid metal chloride. After soaking in water to hydrolyze the metal chloride to metal oxide, the furnace is fired at high temperature to form the carbide. Three metal chlorides, TiCl(,4), MoCl(,5) and WCl(,6), were used to apply TiC, MoC and WC coatings, respectively. Experimental details of the coating procedures are given.

Characterization of the various coatings was carried out using ESCA, …

Isolation And Characterization Of Arginase Isozymes From Bovine Liver And Brain, Christina Carr

Doctoral Dissertations

A chromatographic method was developed to isolate arginase isozymes from bovine brain and liver. The purified proteins were characterized as to their native molecular weight, subunit structure, amino acid composition, hexose content, behavior on disc gel electrophoresis, and reaction with polyclonal antibodies raised against a liver arginase antigen. An arginase-specific messenger RNA preparation was also isolated from liver polysomes using immunological techniques.

Two liver and four brain arginases were purified, having similar native molecular weights, yet different subunit compositions, and displaying varying affinities for the Mn('2+) ion that is required for complete enzymatic activity. The amino acid compositions of all …

Flow Systems For Clinical Analysis Using Immobilized Enzymes And Chemiluminescence Detection (Chromium, Glucose), Jerome L. Mullin

Doctoral Dissertations

Analytical systems used in a clinical setting should offer high sample throughput and eae of operation, while at the same time providing selective, sensitive, accurate and precise determinations of clinically important analytes. Described in this study are two flow systems based on chemiluminescence (CL) detection that provide the features important in a practical clinical method: a flow injection analysis (FIA) system and a two phase flow system. Both systems take advantage of the specificity of enzyme reactions.

FIA systems for the determination of Cr(III) and glucose, based on luminol CL were developed. The Cr(III) system used EDTA as a masking …

Synthesis And Evaluation Of Potential Photoaffinity Inhibitors Of The Human Red Blood Cell Anion Transport System., Jameel. Tajwar

Electronic Theses and Dissertations

Three 4-azidobenzenesulfonates were studied as potential reversible and irreversible inhibitors (photoaffinity labeling reagents) of the human erythrocyte anion exchange system by monitoring their effect on the rate of {('35)S}-sulfate self-exchange at equilibrium. In the dark 4-azido, 2-nitro-4-azido, and 3,5-diiodo-4-azidobenzenesulfonates were reversible inhibitors of sulfate self-exchange with 50% inhibition concentrations (ID(,50) values) of 8.6 (+OR-) 0.46, 0.86 (+OR-) 0.007 and 0.40 (+OR-) 0.004 mM, respectively. If the compounds were first photolyzed at 350 nm and then checked as reversible inhibitors the first two were less potent (ID(,50)'s doubled) while the diiodo compound became a much more potent inhibitor. Photolysis at 350 …

Structural And Regulatory Studies On Rabbit Muscle Phosphofructokinase., Ella Lee Kelley

LSU Historical Dissertations and Theses

Rabbit muscle phosphofructokinase (EC 2.7.1.11; PFK) undergoes a time dependent lag in activity before attaining maximal catalytic velocity. This phenomenon, termed hysteresis, is evident when the enzymatic reaction is initiated with one of the substrates, fructose 6-phosphate (F 6-P). The lag is not manifested with initiation of the reaction by the other substrate, ATP, or with the enzyme. The length of the lag was found to be dependent upon enzyme concentration, pH, concentration of F 6-P, and the presence of inhibitors or activators in the incubation medium. A model is proposed which ascribes this phenomenon to a bisphosphate induced conformational …

Synthesis And Characterization Of Novel Pyridine And Dipyridine Metallocyclic Palladium Complexes., Wallace Earl Puckett

LSU Historical Dissertations and Theses

The synthesis of palladocycles containing trans and cis C-metal anionic sigma bonds has been accomplished. The trans ligands were prepared from 2,6-bis(chloromethyl)pyridine and alkyl malonates by a base catalyzed S(,N)2 reaction. This cis-ligands were formed by a similar reaction but using 6,6'-bis(chloromethyl)-2,2'-dipyridine as starting halide. The synthesis of the latter chloro compound is discussed in detail. The trans complexes were prepared by base mediated cyclometallation on PdCl(,2)(PhCN)(,2) in aqueous ethanol with added pyridine. This cis metallocycles were formed by a similar displacement reaction on PdCl(,2) in acetonitrile but using a heterogeneous base (K(,2)CO(,3)) and a stoichiometric amount of AgNO(,3). Full …

Morphine Levels In Brain Tissue Of Heroin Addicts., Eileen Mercedes. Pare

Electronic Theses and Dissertations

In this study a relatively simple and efficient extraction and derivatization procedure has been used to extract a metabolite of heroin, morphine, from brain tissue. The bis(O-tri-methylsilyl) morphine derivative formed is analyzed by gas chromatography using a 3% OV-17 column and a flame ionization detector. With the procedure as described it is possible to determine as little as 0.13 (mu)g of morphine per gram of brain tissue. The concentration of morphine in the blood of heroin addicts who die as a result of their addiction is often no higher than the level of those who do not die as attested …

4-Deoxy-4-Fluoro-D-Glucose: A Novel Membrane Probe In Pseudomonas Putida., Tony. D'Amore

Electronic Theses and Dissertations

Glucose grown whole cells of Pseudomonas putida do not oxidize 4-deoxy-4-fluoro-D-glucose (4FG). Instead, an extensive release of fluoride ion occurs in which no defluorinated sugar could be detected. Cytoplasmic membrane vesicles and cell-free extracts from this organism oxidize 4FG to the extent of 1 mol oxygen mol substrate('-1) with retention of the carbon-fluorine bond. The defluorination reaction displays saturation kinetics with an apparent K(,m) of 3.9 mM and an apparent V(,max) of 1 nmol fluoride mg protein('-1) min('-1). The reaction is inhibited in the presence of glucose, gluconate or 2-ketogluconate. Growth of cells on gluconate or 2-ketogluconate does not affect …

The Metabolism Of 3-Deoxy-3-Fluoro-D-Glucose By The Fat Body And Flight Muscle Of Locusta Migratoria., Moses Yawo. Agbanyo

Electronic Theses and Dissertations

The metabolism of 3-deoxy-3-fluoro-D-glucose (3FG) by flight muscle and fat body homogenates of locusts was investigated by initially examining the extent of oxygen consumption with 3FG as substrate. 3FG was not only found to be metabolised by both homogenates at a much slower rate (compared to glucose), but also inhibited oxygen consumption from glucose. The presence of aldose reductase (EC.1.1.1.21, alditol: NADP('+) 1-oxidoreductase), and sorbitol dehydrogenase EC.1.1.1.14, alditol:NAD('+)5-oxidoreductase) enzymes have been shown to be present in the flight muscle of locusts, with the flight muscle enzymes exhibiting a higher affinity for their respective natural substrates compared to the fat body …

Multipole Relaxation In Collisions Of 4(2)P Potassium Atoms With Nitrogen And Hydrogen., Randolph William Derek Berends

Electronic Theses and Dissertations

Source: Masters Abstracts International, Volume: 40-07, page: . Thesis (M.Sc.)--University of Windsor (Canada), 1983.

Oxidative Insertion Reactions Of Non-Aqueous Solutions Of Indium(I) Halides., Clovis. Peppe

Electronic Theses and Dissertations

Indium(I) halides (InX) dissolve in toluene containing certain neutral donor ligands below ca. 0(DEGREES)C. The simplest solute species in InBr-toluene-N,N,N',N'-tetramethylethylenediamine (tmen) is InBr.3tmen, but the solution slowly precipitates solid InBr. 1/2tmen. Disproportionation of InX occurs above 0(DEGREES)C, yielding indium metal and In('II) or In('III) complexes, depending on X and the neutral ligand. In solution, InX (X = Cl, Br, I) can oxidatively insert into the In('III)-Y bond of InY(,3) (Y = Br, I) in toluene-dichloromethane-tmen to give neutral tmen adducts of In(,2)XY(,3). Vibrational spectroscopy and n.m.r. studies suggest that the structures involve X(Y)In-InY(,2) kernels, and this was confirmed by the …

Part I: Diels-Alder Reactions Of Heterosubstituted Dienes And Dienophiles. Part Ii: Enamines And Iminium Salts From Amido-Acids., Lilianna Zofia. Pillon

Electronic Theses and Dissertations

The Diels-Alder reaction of 3-carbomethoxy-2,5-dihydrothiophenes with butadiene or isoprene yielded bicyclic thiolanes. The isomeric distribution of the adducts was assigned using cmr data. 3-Acylamino-2,5-dihydrothiophenes were oxidized to sulfones and formed dienes by thermal sulfur dioxide elimination. Heating these sulfones in the presence of maleic anhydride yielded the Diels-Alder adducts in good yields. The cycloaddition reaction of diethyl (alpha)-carbomethoxyvinylphosphonate with isoprene yielded the adduct in 95% yield and as one isomer. An attempt to prepare (alpha)-carbomethoxyvinylphosphonic acid diamide which could be used as a dienophile in the Diels-Alder reaction was unsuccessful. C- and N-((omega)-carboxyalkyl) lactams were prepared and distilled with soda-lime …

Reduction And Alkylation Of 1,3-Oxathiolan-5-Ones As A Route To Alpha-Mercaptoaldehydes., Maqbool A. Siddiqui

Electronic Theses and Dissertations

Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1983 .S544. Source: Masters Abstracts International, Volume: 40-07, page: . Thesis (M.Sc.)--University of Windsor (Canada), 1983.

Polymeric Catechols., Supon Chotiwana

LSU Historical Dissertations and Theses

Polymeric catechols have been synthesized by two general procedures: (a) incorporation of catechol synthons into preformed polymers, or (b) synthesis and polymerization of a monomer containing a formal-protected catechol substituent. The utilization of condensation polymers containing oxy-phenylene repeat units as alternative supports to polystyrene has been evaluated. The techniques of functionalization of the polymers via chloromethylation 1,4-bis(chloromethoxy)butane were highlighted. The effects of concentration, reaction time, and types of Lewis acid catalysts on the extent of chloromethylation were studied. Incorporation of catechol synthons such as 1,3-benzodioxole, 2,2-dimethyl-1,3-benzodioxole, or o-phenylene carbonate into the polymeric matrices having oxy-1,4-phenylene backbone via the Friedel-Crafts reactions …

Equine Infectious Anemia Virus: Characterization Of Virion Polypeptides And The Biochemical Nature Of Antigenic Variation., Bharat Savailal Parekh

LSU Historical Dissertations and Theses

The polypeptide composition of purified radioactively labeled equine infectious anemia virus (EIAV) was investigated using high-resolution sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and guanidine hydrochloride gel filtration (GHCl-GF) to catalog key biochemical properties including molecular weights, stoichiometry, isoelectric points and modifications (glycosylation or phosphorylation). The results of these studies indicate that EIAV contains four major nonglycosylated proteins (p26, pp15, p11, and p9) and two glycoproteins (gp90 and gp45), which together account for greater than 95% of the total virion protein. Four minor polypeptides (p70, p61, p30, and p23) of unknown significance were also detected reproducibly. Comparisons of the major purified …

Synthesis And Characterization Of Ketone And Ketal Coronands Containing 2,6-Pyridino And/Or 6,6'-(2,2'-Dipyridino) Subunits., Hellen Connie Rowland Taylor

LSU Historical Dissertations and Theses

Pyridyllithium reagents were employed in the synthesis of 6-substituted bis(2-pyridyl) ketones and 6,6'-disubstituted 2,2'-dipyridines. The resulting compounds were used in the attempted preparation of pyridine analogues of simple corrins. Coronands were generated from 2,2-bis(6'-bromo-2'-pyridyl)-1,3-dioxolane. Hydrolysis of the protecting dioxolane gave the corresponding ketone coronands, which could be reduced to macrocyclic carbinols with sodium borohydride. Although these compounds would not complex transition metal ions, several were observed to sequester neutral molecules. In particular, the hexaethylene glycol ketone coronand was proven by X-ray diffraction methods to encircle a molecule of water. Electron-poor aromatic ketones were discovered to decarbonylate under mild, basic conditions. …

Rydberg States Of Polyatomic Molecules: Multichannel Approaches For The Simple Halides., John Arthur Dagata

LSU Historical Dissertations and Theses

A major portion of the high resolution photoabsorption spectrum of methyl iodide in the region between 49000 and 77000 cm('-1) has been analyzed by methods based on multichannel quantum defect theory (MQDT). Nearly all bands in this energy region can be assigned as members of molecular rydberg series which converge to the two lowest ionization limits of the molecule. However, it is also found that the Born-Oppenheimer separability of the totality of electronic surfaces is not nearly as complete as might be implied by the above results. Specifically, a nonrydberg, valence electronic state is shown to interact with the rydberg …

Photoelectron Studies Of Methylated And Perfluoromethylated Germanium Derivatives., Krystyna Grazyna. Gorzelska

Electronic Theses and Dissertations

The XPS spectra of perfluoromethylgermanes, (CF(,3))(,n)GeX(,4-n): n = 1(--->)4; X=H,F,Cl,Br,I,CH(,3), were studied in order to determine core-level binding energies of all atoms in these molecules. The inductive effect of the CF(,3) group was determined from the chemical shifts to be close to those of bromine and chlorine atoms. The partial charges calculated using the EESOP method correlate well with the binding energies and lend support to the conclusion that the effective electronegativities of the CF(,3) group, chlorine, and bromine are fairly similar in these compounds. The He(I) and He(II) spectra, recorded within the region 8 to 25 eV, were …

Theoretical And Experimental Studies In Visible Laser Spectroscopy, Akira Brian Yamashita

Digitized Theses

In this thesis, two different aspects of the interaction of radiation with molecules are studied. First, a previously-derived exact solution to the time-dependent Schroedinger equation describing the interaction between a sinusoidally-oscillating field and an N-level atomic or molecular system is used to examine the temporal and steady-state behaviour of a five-level model molecular system. Secondly, the technique of polarization labelling spectroscopy is used to study the E 0(,g)('+) state of the iodine molecule.;The behaviour of the five-level system, consisting of a ground state and four "nearly degenerate" excited states, is studied for various experimental conditions, and for single- and three-photon …

Mechanisms Of Reactions Of Alkenesulfonyl And 2-Substituted Ethanesulfonyl Chlorides, John Henry Hillhouse

Digitized Theses

This thesis describes the mechanisms of the reactions of some simple alkenesulfonyl chlorides and 2-substituted ethanesulfonyl chlorides with tertiary amine bases in aqueous and organic media.;Chapter 1 describes the reactions of ethenesulfonyl chloride and trans-1-propene-1-sulfonyl chloride with water in the presence and absence of substituted pyridines. The former reactions are concluded to proceed by S(,N)2' attack of the pyridine based on the sulfonyl chloride to generate ultimately a pyridine betaine and the pyridinium alkenesulfonate. The formation of the alkenesulfonate anion from the alkenesulfonyl chloride by reaction of the pyridine base corresponds to the first well-established example of a vinylogous nucleophilic …

Adsorption Of Cations At The Sulphide/Water Interface, Gilles Elziar Jean

Digitized Theses

The adsorption of aqueous metal ions on various sulphide minerals was studied as a function of time, pH, surface composition and chemical speciation.;In the first part of this work (Chap. 3) the reaction between various types of gold solutions and several minerals was followed using XPS and SEM. Gold from chloro auric solutions was reduced quickly from Au(III) to Au(O) by every sulphide mineral studied. SEM showed the gold to be unevenly distributed on the surface in the form of agglomerates. Oxide minerals did not reduce gold to any great extent. The gold was shown to adsorb on the sulphide …