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Full-Text Articles in Physical Sciences and Mathematics
New Synthetic Transformations Utilizing Silyloxyallyl Cations And Epoxonium Ions As Reactive Intermediates, Alexander Houston Cleveland
New Synthetic Transformations Utilizing Silyloxyallyl Cations And Epoxonium Ions As Reactive Intermediates, Alexander Houston Cleveland
LSU Doctoral Dissertations
The development of new chemical transformations is of paramount importance in organic chemistry. In fact the study and creation of new reactions often uncovers new chemical reactivities and creates a new area of chemistry. The purpose of this dissertation is to present the development of new synthetic reactions that were uncovered through previous discoveries. Additionally the underlying theme of this work relies on the intermediacy of cationic reactive intermediates such as silyloxyallyl cations and epoxonium ions. Chapters 1 and 2 present the reactivity of novel silyloxyallyl cations. These cationic species are generated via the mild ionization of a-hydroxy silylenol ethers …
Hydroformylation And Aldehyde-Water Shift Catalysis By Dirhodium Tetraphosphine Complexes, Marshall Douglas Moulis
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 …
Synthetic Approach Towards P3eht-B-Pss Conjugated And Ionic Block Copolymer, Zhaoyuan Liu
Synthetic Approach Towards P3eht-B-Pss Conjugated And Ionic Block Copolymer, Zhaoyuan Liu
LSU Master's Theses
This work is focused on the design, synthesis and characterization of block copolymers (BCPs) containing both conjugated and polyelectrolyte blocks. This type of rod-coil BCP is considered to have microphase separation which is different compared to coil-coil BCPs. The conjugated block used for studies is regioregular poly(3-alkylthiophene) (P3AT), which can be synthesized by Grignard metathesis (GRIM) polymerization. The polyelectrolyte block used is polystyrene sulfonate with well-defined structure, which can be synthesized by atom transfer radical polymerization (ATRP). Chapter II is focused on evaluation of synthetic routes for P3EHT-b-PSS, including using bifunctional initiator to synthesize both blocks, and separately synthesizing end-functionalized …
Visible Light And Electron Transfer Chemistry For O-Glycosylation And Remote Hydroxylation, Mark Louis Spell
Visible Light And Electron Transfer Chemistry For O-Glycosylation And Remote Hydroxylation, Mark Louis Spell
LSU Doctoral Dissertations
This dissertation focuses on the synthesis of dauer pheromone analogs for biological evaluation, the development of visible light promoted O-glycosylation methods and the development of an Ir(ppy)3 catalyzed C-H hydroxylation method. Chapter 1 describes the synthesis of dauer pheromone analogs. C.elegans is a small nematode that enters a dauer stage when encountering unfavorable environmental conditions. The dauer stage is initiated by the nematodes chemosensation of the dauer pheromone caused by the down regulation biochemical pathways TGF-â and IGF-1. These biochemical pathways are also seen in Homo Sapiens and play a role in a number of biological processes. Understanding how these …
Synergistic Properties-Driven Synthesis Of Aluminides, Antiomonides, And Bioceramics, Pilanda Watkins-Curry
Synergistic Properties-Driven Synthesis Of Aluminides, Antiomonides, And Bioceramics, Pilanda Watkins-Curry
LSU Doctoral Dissertations
The synthesis, characterization, and properties of selected intermetallics and ceramic materials are presented in this dissertation. In our quest to grow single crystal intermetallics from the metal flux technique, new strategies were employed to avoid thermodynamically stable phases and to ensure sample homogeneity of the crystalline product for structure elucidation and accurate measurements of their magnetic and electrical properties. The relationship between the complex crystal structures and magnetic properties are reported for LnCo2Al8 (Ln = La-Nd, Sm, Yb), CeCo2-xMnxAl8 (0 < x < 1), and Pr2Fe4-xCoxSb5 (1 ≤ x < 3). The discovery of magnetic frustration in LnCo2Al8 (Ln = Ce, Nd) and complex magnetic ordering coupled with large positive magnetoresistance of up to 150% and 60% at 200 K with relatively low field of H = 1 T in Pr2Fe4-xCoxSb5 (x ≈ 2 and 2.5) is also reported. The demand of new inorganic solid materials as scaffolds for the engineering of bone tissue has led to the synthesis of calcium magnesium silicates such as, diopside (CaMgSi2O6), akermanite (Ca2MgSi2O7), monticellite (CaMgSiO4), and merwinite (Ca3Mg(SiO4)2)) for studying dimensionality and mechanical properties. This dissertation highlights the synergism of solid state chemistry at the interface of condensed matter physics and biological engineering. The discovery of compounds with tunable magnetic, electrical, and mechanical properties will be described herein.
Nanoscale Gumbos: Size-Control, Characterization, And Applications As Enantioselective Molecularly Imprinted Polymers And Fluorescent Materials, Suzana Hamdan
LSU Doctoral Dissertations
Nanomaterials derived from a group of uniform materials based on organic salts (GUMBOS) have been introduced into the scientific literature through many analytical, biological, and technological applications. These nanomaterials, referred to as nanoGUMBOS, have been shown to display a number of interesting properties including fluorescence, magnetism, tumor targeting, and optoelectronic properties. Herein, we present major studies on nanoGUMBOS including synthesis and size-control, chiral molecular imprinting in polymers, as well as investigation of optical properties and quantum yield of fluorescent semiconductor-based nanoGUMBOS. Various strategies were introduced for production of well-defined nanoGUMBOS. Specifically, several methods based on sonochemistry, microwave, cyclodextrin, and surfactant-assisted …
Synthesis With Hypergraphs, Christopher Thomas Alvin
Synthesis With Hypergraphs, Christopher Thomas Alvin
LSU Doctoral Dissertations
Many problems related to synthesis with intelligent tutoring may be phrased as program synthesis problems using AI-style search and formal reasoning techniques. The _x000C_first two results in this dissertation focus on problem synthesis as an aspect of intelligent tutoring systems applied to STEM-based education frameworks, specifically high school geometry. Given a geometric _x000C_figure as input, our technique constructs a hypergraph representing logical deduction of facts, and then traverses the hypergraph to synthesize problems and their corresponding solutions. Using similar techniques, our third result is focused on exhaustive synthesis of molecules. This synthesis process involves bonding sets of basic, molecular `fragments' …
Synthesis, Characterization And Biological Studies Of Carboranyl-Porphyrin Bioconjugates For Treatment Of Brain Tumors, Naga Venkata Satya Dinesh Kumar Bhupathiraju
Synthesis, Characterization And Biological Studies Of Carboranyl-Porphyrin Bioconjugates For Treatment Of Brain Tumors, Naga Venkata Satya Dinesh Kumar Bhupathiraju
LSU Doctoral Dissertations
Chapter 1 gives a brief introduction to brain tumors, approaches to deliver drug across the blood brain barrier (BBB), boron neutron capture therapy (BNCT) for brain tumors, application of carboranyl derivatives in attempt to treat brain tumors using BNCT. Chapter 2 involves synthesis, characterization and toxicity studies (In vitro and In vivo) of high boron containing pegylated cobaltabisdicarbollide porphyrin for treatment of brain tumors using BNCT. To improve the selectivity towards brain tumors we attempted conjugate several peptides to this non-toxic pegylated cobaltabiscabollide porphyrin. In vivo studies were conducted in collaboration with Dr. David G. Baker at LSU veterinary Medicine. …
Synthesis, Cellular Studies, And Computational Analysis Of Porphyrin And Bodipy Conjugates With Affinity For Epidermal Growth Factor Receptor, Alecia Michelle Mccall
Synthesis, Cellular Studies, And Computational Analysis Of Porphyrin And Bodipy Conjugates With Affinity For Epidermal Growth Factor Receptor, Alecia Michelle Mccall
LSU Doctoral Dissertations
Chapter 1 is a description of the basic fundamental concepts of porphyrins and BODIPYs, (including synthetic methodologies), a general mechanism of the processes of EGFR, and computational concepts that are elaborated upon in future chapters. Chapter 2 is a discussion solely on the porphyrins that were synthesized to be used as fluorophores for EGFR-targeted conjugates, both peptidic and non-peptidic. The porphyrins were primarily synthesized via the Lindsey method as well as by O-alkylation of tetrahydroxy porphyrins. Synthesis of PEG linkages are discussed as well through three methodologies. Chapter 3 is a presentation of the synthesis, characterization, cellular studies, and computational …
Syntheses And Characterization Of Water-Soluble Phythalocyanines For Diagnosis And Treatment Of Cancer, Benson Getenga Ongarora
Syntheses And Characterization Of Water-Soluble Phythalocyanines For Diagnosis And Treatment Of Cancer, Benson Getenga Ongarora
LSU Doctoral Dissertations
Ongarora, Benson Getenga, B.S., Moi University, 2005 Doctor of Philosophy, Fall Commencement, 2012 Major: Chemistry Syntheses and Characterization of Water-Soluble Phthalocyanines for Diagnosis and Treatment of Cancer Dissertation directed by Professor M.Graҫa H. Vicente Pages in dissertation, xi. Words in abstract, 251. ABSTRACT Chapter 1 describes the general properties of phthalocyanines, synthesis of metallo-phthalocyanines, their photophysical features and their uses. The concepts of PDT and targeted therapeutics are also introduced. Chapter 2 describes the syntheses, characterization, photophysical studies and biological evaluation of cationic phthalocyanines. The trimethylaminophenoxy substituted phthalocyanines were synthesized through statistical condensation method, which gave a statistical mixture of …
Total Synthesis Of A Virotoxin And Analogs For Conformational Studies, Benson Jumba Edagwa
Total Synthesis Of A Virotoxin And Analogs For Conformational Studies, Benson Jumba Edagwa
LSU Doctoral Dissertations
This dissertation describes the first total synthesis of alloviroidin in trace amounts, along with that of three analogs containing L-proline (Pro), trans-3-hydroxyproline (3-Hyp) or cis-4-hydroxyproline (4-hyp) residue substituting for 2,3-trans-3,4-trans-dihydroxyproline in the natural product. We report herein an efficient strategy that provides a dipeptide containing a (2S,4S)-4,5-dihydroxyleucine (dihyLeu) residue, including a diastereoselective dihydroxylation. Nα-Carbobenzyloxy-(2S)-4,5-dehydroleucine was coupled with valine ethyl ester to give a dipeptide that was subjected to a Sharpless asymmetric dihydroxylation to introduce the diol. The relative configuration at C4 was assigned as S by X-ray crystallography after derivatization as an α-amino-γ-lactone hydrochloride salt. The preparation of the 2-(methylsulfonyl)tryptophan …
Understanding The Selective Detection Of Homocysteine And Studies Toward The Synthesis Of Vinigrol, Dong Wang
Understanding The Selective Detection Of Homocysteine And Studies Toward The Synthesis Of Vinigrol, Dong Wang
LSU Doctoral Dissertations
The first part of the work is dedicated to the selective detection of Homocysteine (Hcy). In order to better understand this colorimetric detection method, a thermodynamic model for the pH dependence of the effective reduction potential of Hcy derived á-carbon radicals has been proposed. And using viologen indicators of varying reduction potentials, we demonstrate that colorimetric changes occur at experimental pH values consistent with the model. The one-carbon bridge stereochemistry of bicyclo[3.3.1]nonane framework is critical to make the third ring of the tricyclic precursor of vinigrol. We studied this stereochemistry carefully and found that the major diastereomer formed from Robinson …
Task Specific Ionic Liquids For Enantiomeric Recognition And Nanomaterials For Biomedical Imaging, David Kipkogei Bwambok
Task Specific Ionic Liquids For Enantiomeric Recognition And Nanomaterials For Biomedical Imaging, David Kipkogei Bwambok
LSU Doctoral Dissertations
Ionic liquids (ILs) are organic salts that melt at or below 100°C. Interest in ILs continues to grow due to their unique properties such as lack of measurable vapor pressure, high thermal stability, tunability and recyclability. The first part of this dissertation explores the use of chiral ionic liquids (CILs) for enantiomeric recognition of chiral analytes using fluorescence spectroscopy. Chiral analyses continue to be a subject of considerable interest primarily as a result of legislation introduced by the Food and Drug Administration. This has led to an increased need for suitable chiral selectors and methods to verify the enantiomeric forms …
Xanthene/Benzoxanthene Dyes: Novel Synthetic Metholologies, Applications In Molecular Recognition, Cellular Imaging And The Design Of A Tunable White (Rgb) Light Emitter, Youjun Yang
LSU Doctoral Dissertations
My graduate work has focused on the development of new fluorophore materials towards addressing several interdisciplinary research problems. Selective detection of sialic acid via a boron-amide interaction. Concentration changes of sialic acid can be monitored ratiometrically in the visible region using a boronic acid based chemosensor. The technique shows great promise for the detection of sialic acid, a critical cell surface residue involved in cancer, graft rejection and virulence in certain bacteria. There is no interference from commonly occurring oligosaccharides, aminosugars and most carboxylic acid-containing compounds. Improved synthetic methodology and studies of novel molecular probe architectures. I have developed a …
Synthesis And Functionalizations Of Tetrapyrrole Derivatives, Lijuan Jiao
Synthesis And Functionalizations Of Tetrapyrrole Derivatives, Lijuan Jiao
LSU Doctoral Dissertations
Chapter 1 of this Dissertation presents a brief overview of the history of tetrapyrrole derivatives and of their fundamental properties. Overviews of porphyrins, benzoporphyrins, chlorins and porphycenes are presented. Work presented in Chapter 2 through Chapter 4 mainly focuses on the syntheses and functionalization of chromophore-extended porphyrin derivatives. Several new synthetic routes for the syntheses and functionalizations of extended porphyrins either at the β-position or at the meso-position of porphyrin are developed. From these improved synthetic routes, the regio-selective syntheses of porphyrin derivatives are described. Chapter 2 mainly focuses on the syntheses of β,β'-fused methylenepropanoporphyrins and related porphyrin dimers. Chapter …
The Stereoselective Synthesis Of The Butyrolactone-Bridged [8-5-5] Tricyclic Ring Systems Of (+/-)-Asteriscanolide Via The Titanium-Mediated Hetero-Pauson-Khand Reaction, Mohamed G. Sherriff
The Stereoselective Synthesis Of The Butyrolactone-Bridged [8-5-5] Tricyclic Ring Systems Of (+/-)-Asteriscanolide Via The Titanium-Mediated Hetero-Pauson-Khand Reaction, Mohamed G. Sherriff
LSU Doctoral Dissertations
The stereoselective construction of the tricyclic ring system of asteriscanolide from cyclooctadiene has been achieved. The synthesis involves two main steps; the synthesis of the aldehyde precursor(5)and the titanium-mediated cabocyclization of 5 to make the three rings of 43 stereoselectively.
Synthesis Of Symmetric And Asymmetric Water-Soluble Porphyrin Derivatives, Caroline Owendi Ongayi
Synthesis Of Symmetric And Asymmetric Water-Soluble Porphyrin Derivatives, Caroline Owendi Ongayi
LSU Doctoral Dissertations
Novel symmetric and asymmetric water-soluble tetrabenzoporphyrin are synthesized in relatively good yields. These compounds are synthesized by the condensation of butanopyrrole with several aldehydes that contain masked water solubilizing groups followed by metal insertion, oxidation and demetallation and deprotection of the masked solubilizing groups. The biological evaluation (in vitro and in vivo) studies are described in addition to the photophysical evaluations of the corresponding compounds. A novel versatile route to the syntheses of novel free-bases and metallo-benzoylbiliverdin is discussed. The treatment of metal free-dodecasubstituted porphyrin with sodium nitrite and trifluoroacetic acid at room temperature in the presence of oxygen affords …
Synthesis And Antibacterial Assessment Of Water-Soluble Hydrophobic Chitosan Derivatives Bearing Quaternary Ammonium Functionality, Mrunal R. Thatte
Synthesis And Antibacterial Assessment Of Water-Soluble Hydrophobic Chitosan Derivatives Bearing Quaternary Ammonium Functionality, Mrunal R. Thatte
LSU Doctoral Dissertations
Chitosan is a naturally occurring, bio-degradable, non-toxic, non-allergenic bio-polysaccharide derived from chitin, found in abundance in nature. Studies aimed at deriving newer applications of chitosan are hence of interest. Among these, one of the focuses of investigations is aimed at excellent antimicrobial activity demonstrated by chitosan. In this context, certain quaternary ammonium derivatives of chitosan have been shown in the past to be highly effective antibacterial materials. In the present study, substituted chitosan derivatives were synthesized and further quaternized using Quat-188 to produce water soluble derivatives at neutral pH. The antibacterial assessments of the quaternized derivatives of substituted chitosan were …
The Syntheses Of Novel Indicators And Materials For Chiral Separation, Rolanda Johnson
The Syntheses Of Novel Indicators And Materials For Chiral Separation, Rolanda Johnson
LSU Doctoral Dissertations
The colorimetric properties of resorcinarene solutions had not been fully investigated since von Baeyer's initial synthesis. We find that the solutions containing resorcinarene macrocycles develop color upon heating or standing. In the presence of saccharides, these solutions exhibit significant color changes which are readily observable by visual inspection. We determined that the solution color is due to macrocycle ring opening and oxidation. The optical responses to saccharides are due to complexation of the sugar with the acyclic chromophores. We have applied these mechanistic insights towards the challenging problems of the visual detection of saccharides and other important biologically analytes. In …