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Identification Of Fibroblasts As A Major Site Of Albumin Catabolism In Peripheral Tissues, Jeffrey L. Strobel, Susan G. Cady, Thomas K. Borg, Louis Terracio, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

Rat serum albumin has been labeledw ith dilactitollZ5I- tyramine,( 12‘I-DLT) a radioactive tracer which remains entrappedw ithin lysosomes following cellular uptake and degradation of the carrier protein. Similar kinetics of clearance from the rat circulation were observed for albumin labeled conventionally with lZsI or 12‘I-DLT-albumin, both proteinhsa ving circulating half-lives of -2.2 days. In contrast, the recovery of whole body radioactivity had half-lives of -2.2 and 5.1 days, respectively, for the two protein preparations, indicating substantial retention of degradation products derived from catabolism of ”‘I-DLT-albumin. Measurement of total and acid-soluble radioactivity in tissues 2 or 4 days after injection of …

Identification Of N Epsilon-Carboxymethyllysine As A Degradation Product Of Fructoselysine In Glycated Protein, Mahtab U. Ahmed, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The chemistry of Maillard or browning reactionosf glycated proteins was studied using the model compound, Nu-formyl-W-fructoselysine(f FL), an analog of glycated lysine residues in protein. Incubation of fFL (15 mM) at physiological pH and temperature in 0.2 M phosphate buffer resulted in formation of lVcarboxymethyllysine (CML) in about 40% yield after 15 days. CML was formed by oxidative cleavage of fFL between C-2 and C-3 of the carbohydrate chain and erythronic acid (EA) was identified a s , the split product formed in the reaction. Neither CML nor EA was formed from fFL under a nitrogen atmosphere. The rate of …

Analytical Applications Of Absorption Spectroelectrochemistry At Grazing Incidence, Julian Tyson

Chemistry Department Faculty Publication Series

Analytical applications of spectroelectrochemistry are limited by the short path-length, in the absorbing medium, that can be produced with most light-beam/electrode configurations. This disadvan­tage is overcome for grazing incidence. A cell fitted with glassy-carbon electrodes and used in a conventional spectrophotometer is described and applied to model systems illustrating the use of (a) homogeneous redox reactions, (b) homogeneous redox reaction followed by chemical reaction and (c) electro-deposition followed by stripping into a reagent solution. This last technique is the spectro­electrochemical analogue of anodic-stripping voltammetry.

Peak Width And Reagent Dispersion In Flow Injection Analysis, Julian Tyson

Chemistry Department Faculty Publication Series

No abstract provided.

Interaction Of Polycyclic Aromatic Hydrocarbons With Dissolved And Sediment Associated Humic Materials (Nmr, Fluorescence), Thomas Donald Gauthier

Doctoral Dissertations

A fluorescence quenching method was developed for determining association constants of polycyclic aromatic hydrocarbons (PAH)s with dissolved and sediment bound humic materials. The technique is based upon the observation that PAH fluorescence in aqueous solution is quenched upon association with humic material. Association constants are derived from the fractional decrease in fluorescence intensity as a function of added humic material using Stern-Volmer plots. No separation is required and since the technique involves a ratio measurement the exact concentration of pollutant is not required. Anthracene-humic acid association constants normalized to the fraction of organic carbon in the sorbent (K(,oc)), determined by …

Spectroscopic Studies Of Bacterial Iron-Sulfur Proteins (Electron Paramagnetic Resonance, Magnetic Circular Dichroism)., Deborah Ellen Bennett

LSU Historical Dissertations and Theses

Iron-sulfur proteins play a vital role in metabolism; mediating such life-sustaining processes as aerobic and anaerobic respiration, nitrogen fixation, and photosynthesis. This work employs low temperature magnetic circular dichroism (MCD), electron paramagnetic resonance (EPR), and UV-visible spectroscopy to characterize the iron-sulfur clusters of the following bacterial proteins: Azotobacter vinelandii ferredoxinI, Thermus thermophilus ferredoxin, Escherichia coli nitrate reductase and the rubredoxin and ferredoxin from Clostridium pasteurianum. Novel 3Fe-xS clusters were identified in A. vinelandii FdI, T. thermophilus Fd, ferricyanide treated C. pasteurianum Fd, and E. coli nitrate reductase. The uniformity of the magnetic and electronic properties of these clusters in both …

Spectroscopy And Photochromism Of Triphenylformazan And Its Derivatives., Claudina Veas-Arancibia

LSU Historical Dissertations and Theses

The spectroscopic and photochromic characteristics of triphenylformazan and its derivatives were investigated. These derivatives were formed by adding substituents to the phenyl group attached to the carbon atom of the formazan ring or by replacing this phenyl group with a naphthyl group. Studies of the effect of the concentration, substituent, solvent and temperature on the absorption spectra of triphenylformazan were made. Molecular mechanics calculations were performed to generate two different geometries of triphenylformazan that were used in CNDO calculations to assign the electronic transitions observed in the absorption spectra. In contradiction to what was stated in earlier investigations, the results …

Palladium-Catalyzed Vinylic Substitution Of Aryl Halides On Polymeric Nitrogen Supports., Chia-Hsing Sun

LSU Historical Dissertations and Theses

The structure of typical palladium complexes used as catalysts in organic synthesis is reviewed; particular attention is paid to the systematic study of palladium catalyzed vinylic substitution on a variety of aryl iodides and bromides (Heck-type vinylation). The general conditions of this process, i.e., a homogeneous catalyst operating at moderate temperature, which requires a proton acceptor to complete the catalyst cycle, are conducive to successful development of a polymer-bound catalyst. Using 4-picoline as a ligand under homogeneous Heck-type vinylation conditions. Morpholine is an adequate base to stabilize the catalytic picoline complex when aryl iodides are condensed with styrene. However, sodium …

Fluorescence Of Proanthocyanidin Polymers (Rotational Isomer)., Wolfgang Robert Bergmann

LSU Historical Dissertations and Theses

The lifetimes and quantum yields of proanthocyanidins, monomers and dimers of catechin and epicatechin, were measured. The fluorescence quantum yield and lifetime of the monomers was three times greater in dioxane than in water. The fluorescence decay curves of catechin and epicatechin were found to be fit best by a monoexponential function. The fluorescence decay of dimers of epicatechin and catechin were best fit to a sum of two exponentials. The fluorescence decay curve of a bridged dimer, Procyaninidin A-2, in dioxane was best fit to a monoexponential function. The 400 MHz proton NMR spectra of Procyanidin B-1 decaacetate in …

New Types Of Lanthanide Complexes (Polyatomic Oxides)., Ishenkumba Albert Kasimbazi Kahwa

LSU Historical Dissertations and Theses

Three new types of lanthanide (Ln) complexes, namely, the first examples of homodinuclear macrocyclic lanthanide complexes, novel binary and ternary gaseous polyatomic lanthanide oxides and new lanthanide oxalato complexes are described in chapters one, two and three respectively. The homodinuclear complexes are 2:2 condensation products of 2,6-diformyl-p-cresol and triethylenetetramine templated by Ln(NO(,3))(,3) and Ln(ClO(,4))(,3). The complexes are dimorphic, and are off-white (the more stable form) when they are obtained from dilute solutions and orange if they arise from more concentrated reactants. The complexes were characterized by elemental analysis, fast atom bombardment mass spectrometry (FAB MS), electronic absorption and IR spectroscopy, …

Spectroscopic Studies Of The Metal Centers In Hydrogenases And Carbon Monoxide Dehydrogenase (Nickel)., Isabel Cristina Zambrano

LSU Historical Dissertations and Theses

The biological activation of hydrogen is catalyzed by hydrogenases. An understanding of the mechanism by which hydrogenases act requires the elucidation of the nature and type of metal centers present in the enzymes. Room temperature UV-visible absorption, low temperature magnetic circular dichroism and electron paramagnetic resonance spectroscopies have been used to characterize the electronic and magnetic properties of the iron-sulfur and nickel centers in hydrogenases from Clostridium pasteurianum, Methanobacterium thermoautotrophicum, and Desulfovibrio gigas. In addition, another Ni-containing enzyme, carbon monoxide dehydrogenase from Clostridium thermoaceticum, and D. gigas Ni-substituted rubredoxin were investigated. The results provide evidence for the presence of conventional …

An Investigation Into The Analytical Utility Of Changes In Polarization Accompanying Analytical Derivatization Reactions (Fluorescence), Christopher P. Hallen

Doctoral Dissertations

Derivatization reactions between amines, alcohols and carbonyl groups with various reagents were studied. The goal of the work discussed in this dissertation was to generate basic data to know whether and in what context changes in fluorescence polarization are useful for following analytical derivatization reactions.

Reactions between primary amines and fluorescein isothiocyanate were initially studied. Changes in polarization were observed upon conjugation for many of the amines primarily due to changes in fluorescence lifetime. This reaction was also studied in varying amounts of glycerol to judge the effect of glycerol on the reaction rate. Optimum percentages of glycerol were determined. …

Spectroscopic Studies Of The Interaction Of Anions With Transferrin (Nmr, Pyrophosphate), Susan Keene Swope

Doctoral Dissertations

Kinetic studies of the uptake of iron by transferrin from iron-pyrophosphate indicate that the reaction proceeds via an intermediate mixed ligand complex of the type PP(,i)-Fe-transferrin-CO(,3)('2-). The EPR spectrum of the "intermediate" complex was determined by computer modelling of the kinetic data and deconvolution of the experimental spectra. The distinct spectral characteristics of the intermediate indicate that the coordination environment of the iron is different from that of either of the reactants, consistent with formation of a complex in which iron is coordinated to both transferrin and pyrophosphate.

Studies of the interaction of sodium cyanide with iron(III)-transferrin demonstrate that a …

Preparation, Characterization And Crystal Structures Of Organogermanium Dithiocarbamates And Dithiophosphates., Anil B. Sarkar

Electronic Theses and Dissertations

Thirty-three germanium derivatives of dithiocarbamic acid and dithiophosphoric acid of the general formula R(,n)GeX(,4-n-m)L(,m), where R = CH(,3), C(,4)H(,5), X = Cl, Br, I and L = SC(S)N(CH(,3))(,2), SC(S)N(C(,2)H(,5))(,2), SP(S)(OCH(,3))(,2), SP(S)(OC(,2)H(,5))(,2), with n = 0 - 4, m = 1 - 3, were synthesized in modest to high yields by reacting salts of the acids with the appropriate germanes. The intermediate dithiocarbamate halides were prepared by exchange reactions with trimethylsilyl bromide and iodide. The compounds were characterized by elemental analysis, vibrational and nuclear magnetic resonance spectroscopy, mass spectrometry and by single crystal X-ray structure determinations. In the ('1)H and ('13)C …

Spectral Studies Of Constituents Of Members Of The Family Asteraceae., Karla Ann Wilzer

LSU Historical Dissertations and Theses

A phytochemical investigation of ten species of the genus Aster (Family Asteraceae, Tribe Astereae) was carried out. The study involved the following taxa from the southern region of the United States: A. adnatus, A. concolor, A. dumosus x lateriflorus (a hybrid), A. lateriflorus, A. patens, A. praealtus, A. spinosus, A. subulatus var. ligulatus and A. tenuifolius as well as A. umbellatus from Pennsylvania. The chemical analysis of A. praealtus provided umbelliferone and seven prenylated coumarins of which four were new natural products. A ten-carbon acetylenic compound was isolated from A. spinosus. (DELTA)('7)- Sterols were found in A. adnatus which is …

Modification Of Condensation Polymers., Cholticha Rungaroonthaikul

LSU Historical Dissertations and Theses

The degradation of poly oxy-1,4-phenylene(1-methylethylidene)-1,4-phenylene-oxy-1,4-phenylenesulfonyl-1,4-phenylene (poly(arylether sulfone)), 1, promoted by excess sodium methoxide was evaluated spectrophotometrically. Direct nitration of 1 with ammonium nitrate in trifluoroacetic anhydride produced poly(2-nitroarylether sulfone). The model segment 1 produced by reaction of 2,2'-bis(4-hydroxyphenyl)propane (bixphenol-A) with 7, was nitrated to obtain model segment of 2,2'-bis 3-nitro-4-(4-phenylsulfonyl phenoxy)-phenyl propane. The rate of polymer degradation was estimated by observing the increase in the concentration of phenolate end groups in the presence of sodium methoxide. It was shown that less than 6% degradation of the most reactive polymer, poly(2-nitroarylether sulfone) occurred after one week at 25(DEGREES)C. Comparison of the …

Laser Optogalvanic And Photoacoustic Studies Of Some Atoms And Small Molecules., Phillip Lamar Clancy

LSU Historical Dissertations and Theses

A device designed to perform laser optogalvanic (LOG) measurements on low pressure gases in an electrical discharge has been constructed. The device employs the unique combination of pulsed laser radiation in the visible range, and transverse excitation of a radiofrequency (RF) discharge to obtain high quality spectroscopic data on highly excited atomic and molecular species existing in an electrical discharge. The results of LOG studies on xenon, cesium, and nitrogen are reported. In addition to functioning as a sensitive LOG detector, it has been discovered that the RFLOG device serves admirably as a contractless transducer of the photoacoustic signal. When …

Spectroscopic Studies Of Mitochondrial Iron Sulfur Proteins (Succinate Dehydrogenase, Electron Paramagnetic Resonance, Fumarate Reductase)., Joyce Elaine Morningstar

LSU Historical Dissertations and Theses

Aerobic respiration is linked to oxidative phosphorylation and involves a redox-linked proton translocation across the mitochondrial inner membrane. Deeper understanding of the mechanism of mitochondrial electron transport requires detailed characterization of the redox centers present in respiratory enzyme complexes. A combination of low temperature MCD spectra and magnetization data, with parallel EPR, CD, and UV-visible experiments, has been used to characterize the structural, electronic, and magnetic properties of the iron sulfur centers in respiratory enzymes. The enzymes studied were those associated with electron transport in mammalian mitochondria, with comparative studies of similar enzymes and proteins in heterotropic bacteria. The results …

Characterization Of The Protein And Glycoprotein Components From Antigenically Distinct Strains Of Equine Infectious Anemia Virus., Olivia Salinovich

LSU Historical Dissertations and Theses

Four isolates of equine infectious anemia virus (EIAV) recovered weeks apart from a single experimentally infected Shetland pony (Orrego, 1983) were examined in both antigenic and structural analyses to investigate variation occurring during persistent infection. These four isolates were shown to be antigenically distinct in both serum neutralization assays and in immunoblot analysis with either a polyclonal equine reference antiserum or a panel of virus-specific monoclonal antibodies. Two-dimensional mapping of tryptic peptides of viral components from these isolates revealed that both gp90 and gp45 undergo structural variation during virus replication in a single animal, but that no such structural variation …

Rearrangements Of Alpha-Halosilanes And Conformational Analysis Of Silanes., Rayomand Jal Unwalla

LSU Historical Dissertations and Theses

A number of (alpha)-halosilanes, some which are chiral at carbon, have been prepared. Lewis acid-catalyzed rearrangements and thermal rearrangements were performed on ((alpha)-chloroethyl)diphenylmethylsilane. Both the rearrangements proceed cleanly; the major product is formed by the migration of the phenyl group from silicon to carbon. The rearranged product mixture was subjected to a Kumada-type oxidation in which the silicon-carbon is cleaved stereospecifically. Thus the principle has been established that a clean rearrangement can be carried out in a manner which will allow determination of the stereochemistry at the carbon center. Preliminary kinetic studies of the thermolysis of ((alpha)-chlorobenzyl)dimethylphenylsilanes containing p-substituents in …

Models For The Study Of Intramolecular Interactions: Preparation, Structure And Reactivity Of 2-(2'-Acyloxyphenylethynyl)Benzoic Acids., Michael Allen Oliver

LSU Historical Dissertations and Theses

The hypothesis concerning orientational effects of carboxylate in general-base catalysis is discussed, and the first models that allow proton transfer to the syn lone-pair of the carboxylate during intramolecular general-base catalysis are designed, prepared, and tested. These models use a carbon backbone of two aryl groups linked by a two carbon bridge. The syntheses of 2-(2-hydroxyphenylethynyl)benzoic acid (24) and derivatives used in these studies are described. These derivatives were also needed to evaluate the ethynyl group as the bridge linking the aryls and to aid in the design of more complex models. The hydrolysis of the dichloroacetate ester (26) is …

Photophysics And Photochemical Studies Of Polypyridine Ruthenium (Ii) Complexes., Mario Alberto Ollino

LSU Historical Dissertations and Theses

Stern-Volmer plots for the quenching of luminescence and for the photosubstitution reaction of tris-bipyridylruthenium(II) at 298 K were obtained. The two Stern-Volmer plots were found to be similar; this result is different from that of a previous report, but it agrees well with a general model postulated to represent the photophysical processes of the excited states of polypyridine ruthenium(II) complexes. The temperature dependence of the emission intensities and of the lifetimes of tris-bipyridylruthenium(II), cis-ibspyridyl bis-2,2'bipyridylruthenium(II), and 4,5-diazafluorenyl-bis-2,2'bipyridylruthenium(II) were reinvestigated in order to evaluate the difference in energy between the triplet metal to ligand charge transfer and ligand field excited states. …

Synthesis Of Poly(Vinylcatechols)., Saad Moulay

LSU Historical Dissertations and Theses

5-Vinyl-1,3-benzodioxole, 28, 3,4-dimethoxystyrene, 29, 2,3-dimethoxystyrene, 30, 6-vinyl-1,4-benzodioxane, 31, and 4-vinyl-1,3-benzodioxole, 32 were synthesized and evaluated as poly(vinylcatechol) precursors. Four methods for preparing these monomers were explored. Dehydration of (alpha)-phenethyl alcohols was the best general procedure. Molecular weights as high as 95,000 in the case of poly(2,3-dimethoxystyrene) were achieved in the presence of free radical initiators. The kinetics of free radical polymerization of 2,3-dimethoxystyrene, 30, was studied dilatometrically and the overall rate of the reaction was found to be R(,p) + 2.53 x 10('-2) mol/L min. Radical copolymerizations of monomers 30 and 31 with styrene and methyl methacrylate were examined. The …

The Magnesium(2+)-Dependent Phosphatidate Phosphohydrolase Of Rat Lung, Paul Albert Walton

Digitized Theses

The Mg('2+)-dependent phosphatidate phosphohydrolase (PAPase) activity has been studied in rat lung subcellular fractions, and a malignant cell line (A549) which serves as a model of human Type II pneumocytes. Properties of this activity, which used a chemically-defined substrate of equimolar PC and PA, were equivalent to those found using membrane-bound substrate. Microsomes washed in buffers containing high salt concentrations displayed a decrease in the PAPase which could be quantitatively recovered in the wash supernatant. Mg('2+)-independent activity remained associated with the microsomes under these conditions. These microsomes displayed a reduced capacity to label glycerolipids from ('14)C -glycerol phosphate. Labelling could …

Synthetic, Enzymic And Metabolic Studies Of Deoxyfluoro - Monosaccharides., Samuel Torto. Squire

Electronic Theses and Dissertations

In Part I, a rationale for the synthesis of 4-deoxy-4-fluoro-D-fructose using a combination of chemical and enzymic methods is proposed and undertaken. Partially purified pyranose-2-oxidase (E.C. 1.1.3.10) is isolated from mycelia of Polyporus obtusus and a study of the enzyme specificity undertaken. Pyranose-2-oxidase is specific for the oxidation of glucose to D-arabino-hexos-2-ulose (D-glucosone) with a Km value of 3.2 (+OR-) 0.08mM and a Vmax of 126 (+OR-) 0.02(mu)mol min('-1) mg protein('-1). In contrast, 3-deoxy-3-fluoro-D-glucose is not a substrate for the enzyme. 4-Deoxy-4-fluoro-D-glucose, however, does act as a substrate with a Km value of 5.54 (+OR-) 0.64mM and a Vmax of …

Part I. Electrophile Structure As A Factor In Alkylations Of Camphor Derivatized Glycinates. Part Ii. Pummerer Reactions Of S-Oxides Of 1,3-Oxathiolan-5-Ones And 1,3-Thiazolidin-4-Ones., Randall K. Leavitt

Electronic Theses and Dissertations

Part I. Alkylation reactions of the camphor imine of t-butyl gly- cinate 1 were found to proceed with varing amounts of diastereo- facial selectivity depending on the electronic nature of the alkylating agent. Saturated alkyl halides gave diastereomeric excesses up to 67%. Allylic and benzylic alkylating agents reacted to provide diastereomeric excesses up to 98%. A transition state model which involves a favorable electronic interaction between the pi system of the alkylating agent and the lithium enolaate has been proposed to explain the enhanced diastereoselectivities observed for these types of alkylating agents. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) (UNFORMATTED …

Work Towards The Total Synthesis Of Patchouli Alcohol And Approaches To Cycloseychellene, Murray Douglas Bailey

Digitized Theses

The synthesis of polycyclic compounds usually requires numerous synthetic operations in order to construct the desired carbon skeletons. A simple procedure termed a bicycloannulation allows for the generation of one of these ring systems in one synthetic operation. The tricyclo 3.2.1.0('2,7) octane ring system incorporates a two carbon bridge cross a cyclohexane ring which includes at one end a cyclopropane ring. This tricyclic carbon skeleton is a highlighting feature of a number of terpenoids, including the sesquiterpene cycloseychellene. Beginning with a substituted cyclohexenone, the bicycloannulation allows for the construction of all but one of the rings in this tetracyclic sesquiterpene. …

An Investigation Of Dinuclear Alkylidene-Bridged Carbonyl Complexes, William John Laws

Digitized Theses

The objective of this research was to synthesize binuclear (mu)-alkylidene complexes of manganese or cobalt, to study their chemical properties, and to assess their potential as model intermediates in the Fischer-Tropsch synthesis.;Excess diazoalkane addition to Mn(,2)(CO)(,4)((mu)-CO)((mu)-dppm)(,2) ; dppm = Ph(,2)PCH(,2)PPh(,2), produces 1:1 adducts of formula Mn(,2)(CO)(,4) (mu)-C(O)CHRN(,2) ((mu)-dppm)(,2) (R = H,Me,CO(,2)Et) containing a novel metallacycle derived from coupling of the diazoalkane molecule with a carbonyl ligand. The structure was established by an X-ray analysis of Mn(,2)(CO)(,4) (mu)-C(O)CH(,2)N(,2) ((mu)-dppm)(,2) . Photolysis or thermolysis of each adduct regenerates Mn(,2)(CO)(,4)((mu)-CO)((mu)-dppm)(,2) .;A series of ((mu)-alkylidene)dicobalt complexes was prepared via CO displacement from Co(,2)(CO)(,4)((mu)-CO)(,2)((mu)-dppm) at …

Trinuclear Clusters Of Palladium And Platinum, Brian Richard Lloyd

Digitized Theses

The syntheses of trinuclear clusters, M(,3)((mu)(,3)-CO)((mu)-dppm)(,3) ('2+); M = Pt or Pd; dppm = Ph(,2)PCH(,2)PPh(,2), has been accomplished with the structural features of both the platinum and palladium clusters having been investigated by spectroscopic and x-ray crystallographic structure determinations. The mechanism of formation has been shown to involve the reduction of M(II) monomers through M(I)(,2) dimers to M(2/3)(,3) trimers with parallel oxidation of CO(,(g)) to CO(,2(g)), in aqueous media.;The selective attachment of halide ions to the triply bridging site of Pd(,3)((mu)(,3)-CO)((mu)-dppm)(,3) ('2+) has been established and the equilibrium constants for coordination have been shown to follow the sequence of I('-) …

Studies In Asymmetric Hydrosilation, Ian Douglas Mckay

Digitized Theses

The ligand amphos forms square planar Rh(I) complexes which catalyze the asymmetric homogeneous hydrosilation of ketones in up to 72% optical yield. Initially, modifications of the aminophosphine ligand, N,N-dimethyl-1-(o-(diphenylphosphino)phenyl)ethylamine, amphos, were prepared and their Rh complexes were tested as catalysts for the asymmetric hydrosilation of ketones. In the second approach x-ray crystallography, spectroscopic techniques, and conformational energy calculations were used to investigate the relationship between catalyst shape and efficiency.;Three modifications of the amphos ligand were prepared. In the first two the phenyl substituents on P were replaced by either cyclohexyl groups, dicyphos, or tert-butyl groups dibutphos. In the third modification …