Physical Sciences and Mathematics Commons^™

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.

Oxocarbenium Ion And Alkene Metathesis Strategies For The Synthesis Of Complex Cyclohexanes, Clayton Errol Mattis

Dissertations, Theses, and Capstone Projects

Highly oxygenated cyclohexanes comprise the structures of a number of pharmacologically interesting molecules, including potently bioactive natural products and carbapyranosides. The latter, which are unnatural analogues of carbohydrates in which the ring oxygen of the parent sugar is replaced with a methylene group, have attracted interest as hydrolytically stable mimetics of their parent O-glycosides. This research reports the development of two general methodologies for the synthesis of highly oxygenated cyclohexanes: (1) Oxocarbenium Ion Cyclization (OCC) and (2) Ring Closing Metathasis (RCM).

Chapter one gives a review of the literature on the synthesis for highly oxygenated cyclohexanes.

Previous results from this …

Design, Synthesis, Characterization, And Evaluation Of Surface Modified Boronate Ester Covalent Organic Frameworks, Matthew W. Di Carmine

Theses and Dissertations

Covalent Organic Frameworks (COFs) were first reported in 2005 and are analogous to Metal Organic Frameworks (MOFs), with proposed applications in separation, storage and sequestration. Since COFs are comprised of lighter elements they are considered more advantageous for weight-sensitive applications. However, COFs are susceptible to degradation by weak nucleophiles such as water (i.e. hydrolysis). The Lavigne group has focused on developing structure-property relationships for COFs. It was previously demonstrated that the porosity of the COFs could be tailored by incorporating small alkyl chains on one monomer. Inclusion of these alkylated monomers into COF materials effectively increased the COF hydrophobicity resulting …

Suzuki-Miyaura Reactions Are Used To Synthesize Z-Alkenes From Cyclic Boronic Half-Acids, Daniel Lee French

Undergraduate Honors Thesis Collection

Cis-Alkenes provide the basic structure and reactivity for a variety of compounds, from the common chemicals found in any organic laboratory to advanced drugs used to treat cancer or suppress the immune system (Littke & Fu, 2002). Synthetically, alkenes are also of use in that they serve as a site for further chemistry. Historically, Z-alkenes have been more difficult to synthesize than their E-counterparts (McNulty et al., 2010; Siau, Zhang, & Zhao, 2012). Furthermore, in many reactions, a mixture of E- and Z- conformations of the alkene is produced. Such differences may seem trivial upon first inspection, but because there …

Synthesis And Resolution Of A Substituted Dioxolane From Glycerol, Susannah Dawn Cox

Undergraduate Honors Thesis Collection

Glycerol (Figure 1) is one of the major byproducts in the manufacturing of biofuels. As the interest in biodiesel grows, production of glycerol will also increase. Investigating glycerol's potential as a chemical feedstock could lead to the discovery of new uses for this byproduct created from biofuel production. By developing pathways to use glycerol as a starting material and as a solvent we will be able to synthesize other chemically relevant compounds.

Size-Dependent Interactions Of Metal Nanoparticles With Fluorophores And Semiconductors, Liyana A. Wajira Ariyadasa

Dissertations

In recent years, nanoscale metallic particles have gained considerable interest due to their potential applications in advanced technology. Despite such interest, synthetic procedures that produce gram-scale, well-defined metallic nanoparticles with controlled size and shape, especially with diameters less than 5 nm remains a challenge. Our work has focused on developing synthetic procedures that produce well-defined platinum and palladium metal nanoparticles in the 1-5 nm size range. Thioether ligands were used as stabilizers and resulted in metal nanoparticles with controlled size. The nanoparticles were characterized using transmission electron microscopy (TEM), x-ray diffraction (XRD), selected area electron diffraction (SAED), x-ray photoelectron spectroscopy …

Facile Synthesis And Characterization Of A Thermally Stable Silica-Doped Alumina With Tunable Surface Area, Porosity, And Acidity, Maryam Khosravi Mardkhe

Theses and Dissertations

Mesoporous γ-Al2O3 is one of the most widely used catalyst supports for commercial catalytic applications. The performance of a catalyst strongly depends on the combination of textural, chemical and physical properties of the support. Pore size is essential since each catalytic system requires a unique pore size for optimal catalyst loading, diffusion and selectivity. In addition, high surface area and large pore volume usually result in higher catalyst loading, which increases the number of catalytic reaction sites and decreases reaction time. Therefore, determination of surface area and porosity of porous supports is critical for the successful design and optimization of …

Modified Seed Growth Of Iron Oxide Nanoparticles In Benzyl Alcohol: Magnetic Nanoparticles For Radio Frequency Hyperthermia Treatment Of Cancer, Stanley E. Gilliland Iii

Theses and Dissertations

Iron oxide nanoparticles have received sustained interest for biomedical applications as synthetic approaches are continually developed for precise control of nanoparticle properties. This thesis presents an investigation of parameters in the benzyl alcohol synthesis of iron oxide nanoparticles. A modified seed growth method was designed for obtaining optimal nanoparticle properties for magnetic fluid hyperthermia. With a one or two addition process, iron oxide nanoparticles were produced with crystallite sizes ranging from 5-20 nm using only benzyl alcohol and iron precursor. The effects of reaction environment, temperature, concentration, and modified seed growth parameters were investigated to obtain precise control over properties …

Synthesis, Characterization, And Application Of High Surface Area, Mesoporous, Stabilized Anatase Tio2 Catalyst Supports, Rebecca Elizabeth Olsen

Theses and Dissertations

Nanomaterials have attracted substantial attention in the area of catalysis due to the unique properties they exhibit such as high surface areas, intricate pore networks and unique morphologies. TiO2 has attracted attention as a catalyst since the discovery of its high photocatalytic activity by Fuishima and Honda in 1972. Given its high thermal stability, low cost, low environmental impact, and versatility, TiO2 is a widely used commercial catalyst and catalyst support. TiO2 is used in many applications such as photocatalysis is also an excellent support material for noble metals in a number of oxidative synthesis and pollution-control reactions. Though TiO2 …

Continued Progress Towards Efficient Syntheses Of Cephalostatin North 1 Analogs, Daniel Preston Jamieson

Open Access Dissertations

Jamieson, Daniel P. Ph.D., Purdue University, December 2013. Continued Progress Towards Efficient Syntheses of Cephalostatin North 1 Analogs. Major Professor: PhilipL. Fuchs.

The cephalostatins and ritterazines represent an intriguing class of marine natural products in both structure and biological activity, and the progress towards the synthesis of high valued analogs with a focus on process orientated methodology is described herein. Included in the pages to follow, is the further advancement of the `Red-Ox' strategy toward the highly efficient synthesis of 25-epi-4,15-dihydro-North 1, Chapter 2. A short review focusing on the earlier efforts toward the main synthetic challenges of North 1 …

Synthesis Of Novel Isoprenoid Diphosphate Analogs As Chemical Tools To Investigate Protein Geranylgeranylation, Kayla Jo Temple

Open Access Dissertations

Many proteins require prenylation in order to be biologically functional. Some such proteins include the small Ras and Rho GTPase superfamilies, nuclear lamins A and B, and the kinesin motor proteins CENP-E and F. Prenyltransferase (PTase) inhibition is currently being explored as a possible treatment not only for cancer but for a wide variety of other diseases.

Clinical studies revealed that the effectiveness of farnesyltransferase inhibitors (FTIs) to treat Ras-dependent tumors is determined by which isoform of Ras is overactive. Unfortunately the majority of Ras-dependent tumors have a mutation in either the N- or K-Ras isoforms; both of these isoforms …

Siloles Bearing Coordination-Active 2,5-Substituents: Synthesis, Reactivity, Structural And Spectral Properties., James Bryan Carroll

Dissertations

Siloles, or silacyclopentadienes and other group 14 metalloles are structurally analogous to their all-carbon analogue, cyclopentadiene, except for the heavy group 14 element (i.e., Si, Ge, Sn, and Pb) in the 1-position. The placement of the heavy element in this position allows for unique properties, such as high electron affinity, mobility, and bathochromically shifted optical spectra, as compared to cyclopentadienes, and the relatively low-lying lowest-unoccupied molecular orbital (LUMO) helps to account for these properties. The substituents about the silole have a significant impact on the electronics and properties observed, with 2,5-substituents inducing the most substantive changes. Even as many 2,5-substituents …

Latent Cysteine Residues From Polymers Prepared Via Free And Controlled Radical Polymerizations, Douglas Vincent Amato

Master's Theses

One less commonly used “click” reaction is thiazolidine chemistry. Thiazolidine chemistry is a commonly used reaction used in biological systems because the reaction requires the presence of both cysteine (a common amino acid) and an aldehyde or ketone. If cysteine residues could be incorporated into a polymer then a variety of applications could be developed. Polymers containing free thiols (aka thiomers) have developed in the last decade to become great mucoadhesives. If there was a facile route to control the amount of free thiols along the polymer then more fine-tuned and potentially stronger adhesives could be made. For these reasons …

Synthesis And Immunological Evaluation Of Type I, Type Ii, And Gamma Delta Nkt Cell Antigens, Brian L. Anderson

Theses and Dissertations

The purpose of the immune system is to protect our bodies from infection. One way it accomplishes this task is through the presentation of foreign pathogens to NKT cells. After an antigen is presented to the T cell receptor, activated NKT cells quickly release soluble chemical signals, termed chemokines and cytokines, that modulate the response of the immune system. Due to the immunological relevance of NKT cell activation, we developed and synthesised non-natural analogs of immunostimulatory type I, II, and gamma delta NKT cell antigens. The immunological evaluations of these analogs resulted in identification of sulfatide as a gamma delta …

Synthesis Of Isotopologues And Nanoparticles For Hyper Raman Spectroscopy, Burton K. Mandrell

Chancellor’s Honors Program Projects

No abstract provided.

Facile Synthesis And Improved Pore Structure Characterization Of Mesoporous Γ-Alumina Catalyst Supports With Tunable Pore Size, Baiyu Huang

Theses and Dissertations

Mesoporous γ-alumina is the most extensively used catalysts support in a wide range of catalytic processes. The usefulness of γ-alumina relies on its favorable combination of physical, textural, thermal, and chemical properties. Pore structure properties are among the most important properties, since high surface area and large pore volume enable higher loading of active catalytic phases, while design of pore size and pore size distribution is critical to optimize pore diffusional transport and product selectivity. In addition, accurate determination of surface area (SA), pore volume (PV) and pore size distribution (PSD) of porous supports, catalysts, and nanomaterials is vital to …

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. …

Silylation-Based Kinetic Resolution Of Α-Hydroxy Carbonyl Compounds And Synthesis Of Chiral Isothiourea Catalysts, Yan Zhang

Theses and Dissertations

The thesis describes the silylation-based kinetic resolution for α-hydroxy carbonyl compounds catalyzed by isothiourea catalyst as well as our effort to make novel chiral isothiourea catalyst.

In Chapter 1, general background will be introduced, including chirality, general methods to obtain enantiopure compounds and kinetic resolution. In Chapter 2, the mechanism of the chiral recognition was discussed and a novel isothiourea catalyst was design to investigate the mechanism. The synthesis of the new catalyst was also described in this chapter.

In Chapter 3, the silylation-based kinetic resolution for α-hydroxy carbonyl compounds will be discussed. Since silylation-based kinetic resolution have already been …

Synthesis, Characterization And Application Of Pt Complexes With Pincer Ccc-Bis(Nhc) Ligands, Xiaofei Zhang

Electronic Theses and Dissertations

The unique metallation/transmetallation route for the synthesis of CCC-bis(NHC) pincer ligand supported transition metal complexes was extended to Pt. Several platinum complexes were synthesized. The identity of these complexes was confirmed through multiple technologies, including nuclear magnetic resonance spectroscopy, mass spectroscopy, elemental analysis, thermal analysis, and X-ray crystallography. The intriguing photophysical and thermal properties of these complexes are reported. These complexes were believed to be congeners of materials for organic light emitting diodes (OLEDs).

Synthesis Of Palladium-Based Electrocatalysis—From Pure Metal To Bimetallic Nanoparticles, Haijun Gao

Masters Theses

This thesis focuses on synthesis and characterization of palladium-based nanoparticles. Background information of the research in this thesis is provided in Chapter 1. Preparation and characterization of pure palladium nanoparticles are presented in Chapter 2. A fast and convenient method to prepare ultra small Pd nanoparticles via Pluronic P123 reduction is discussed in detail. Impregnation method and poly method are also studied in this chapter. Chapter 3 reports the studies of these methods to prepare ultra small bimetallic (bimetallic means a mixture of two metals) palladium-based nanoparticles. Oleylamine-mediated method used Pd nanoparticles prepared via P123 reduction as precursor. Ultra small …

Synthesis Of 1,1-Dialkyhydrazines And Their Hydroxyl Radical Degradation In Aqueous Environments, Benjamin F. Strong

Masters Theses

Determination of hydroxyl radical rate constants are essential to ensure adequate degradation of contaminants in wastewater. Hydrazines are an important class of organic contaminants and are the focus of this research. Ten 1,1-dialkylhydrazines are synthesized by the zinc reduction of the corresponding N-nitrosamines. Their hydroxyl radical rate constants are determined using the linear accelerator at the Notre Dame Radiation Laboratory at pH 4, 7, and 10.

Their rate constants are found to depend on the protonation state of the molecule. At pH 4 the molecules are fully protonated and hydrogen atom abstraction is favored from the alkyl chains. At …

The Synthesis And Structural Characterization Of Metal Oxide Nanoparticles Having Catalytic Applications, Stacey Janel Smith

Theses and Dissertations

Nanotechnology is blossoming into one of the premiere technologies of this century, but the key to its progress lies in developing more efficient nanosynthesis methods. Variations in synthetic technique, however, can cause variations in size, structure, and surface characteristics, thereby altering the physical properties and functionality of the particles. Careful structural characterizations are thus essential for understanding the properties and appropriate applications for particles produced by new synthetic techniques.In this work, a new ‘solvent-deficient’ method is presented for the synthesis of an unprecedentedly wide range of metal oxide nanomaterials including at least one metal oxide from each group in Groups …

The Synthesis Of A Homologous Series Of Alkyl Lumazines And Their Application To The Dispersion Of Carbon Nanotubes, William P. Kopcha

Master's Theses

In this thesis, the synthesis of a series of alkyl lumazine surfactants (LC_n) is reported. Their application to the dispersion of both CoMoCAT and HiPco single-walled carbon nanotubes (SWNTs) is examined in detail and the thermal stability and chirality selection properties of dispersions made with these surfactants were compared both between themselves and with an alkyl flavin surfactant (FC₁₂). Lumazine alkyl chain length exhibited some control over the quality and the quantity of SWNTs dispersed. LC₁₀ was deemed most appropriate for comparison with FC₁₂ based on considerations of solubility and nanotube individualization. …

Ferrocene Constrained Helical Peptides Via On-Resin Cyclization, Thomas A. Mcteague

Senior Theses and Projects

Previous research within the Curran group has demonstrated that ferrocene may be used as an organometallic constraint to induce the formation of α-helices in short peptides which traditionally possess undefined conformations. Through strategic placement of lysine residues at the i and i+3 positions within the peptide, such a constraint was accomplished via the crosslinking of the lysine side chains to ferrocene dicarboxylic acid chloride in solution phase synthesis. The aim of this work was to develop a method for solid phase peptide synthesis (SPPS) for the synthesis of these ferrocene-constrained helices. In particular, we seek to develop a method in …

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

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 …

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 …

Design And Synthesis Of Cationic Steroid Antimicrobial Compounds, Synthesis Of Glycolipids Recognized By Natural Killer T Cells And Development Of Tlr-1, Tlr-6 Heterodimer Binders And Studies Of Their Immunology Activities, Yanshu Feng

Theses and Dissertations

Cationic steroid antimicrobial agents (CSAs) are a family of bile acid derivatives. These compounds are amphiphilic and mimic endogenous antimicrobial peptides. The antimicrobial activities of CSA-13 have been investigated and due to portent bactericidal activities and low toxicity, a large amount of CSA-13 is demanded for clinic trails and other antimicrobial applications. During our studies, we optimized the synthetic route of CSA-13, so that it can be prepared at the kilogram, even in tons scale. We investigated three routes and one of them is suitable for industry, because only recrystallization is needed in the synthesis. Natural killer T cells (NKT …

Synthesis Of Resveratrol Ester Derivatives Using Selective Enzymatic Hydrolysis., Marian Osei-Mensah

Electronic Theses and Dissertations

Resveratrol, a naturally derived stilbene, is an interesting compound mostly talked about recently because for its anti-cancer properties. Unfortunately it has some shortcomings due to its low bioavailability and low solubility in water. For this reason, my research is to overcome resveratrol's drawbacks by improving its bioavailability and hydrophilicity. My research is focused on syntheses of novel derivatives of resveratrol such as 3, 5-di-O-isobutyroyl resveratrol and 3, 5-di-O-hexanoyl resveratrol using lipase catalyzed hydrolysis. Therefore, the tri-acylated resveratrols 3, 5, 4'-tri-O-isobutyroyl resveratrol and 3, 5,4'-tri-O-hexanoyl resveratrol were first synthesized.

3,5,4'-tri-O-isobutyroyl resveratrol and 3,5,4'-tri-O-hexanoyl resveratrol were then hydrolyzed using lipase (C. …

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 …