Physical Sciences and Mathematics Commons^™

I. Synthesis Of Ascarosides For Biological Evaluation And Ii. Development Of Visible Light-Promoted Selenofunctionalization And Grafting Of Aryl Iodides, Elizabeth Susan Conner Balapitiya

LSU Doctoral Dissertations

This dissertation focuses on analog synthesis for biological evaluation and visible light promoted method development. Chapter 1 centers upon the synthesis of Caenorhabditis elegans dauer pheromone analogs. C. elegans is a nematode which, in times of environmental stress, enters a dauer stage. Two highly conserved pathways, which play important roles in some diseases in higher organisms, monitor dauer formation: TGF-β and IGF-1. Dauer formation is triggered by the nematode’s chemosensation of the dauer pheromone, consisting of a group of previously-isolated ascarosides. These compounds differ in chain length, saturation, terminal functionality of side chain, ω vs. ω-1 oxygenation and presence of …

Enzyme, Cosolvent, And Substrate Interactions In Ple Hydrolysis Reactions And Evaluation Of The Stability Of An Unnatural Glutathione Analogue, Maureen Elizabeth Smith

Dissertations

Prochiral diester malonates have been hydrolyzed in the presence of Pig Liver Esterase (PLE). Several of the diesters produced the respective half-ester in moderate to high enantioselectivity. A series of cosolvent assays were performed to evaluate the ability of the cosolvent to influence the enantioselective outcome of the hydrolysis reactions. Ethanol produced the largest changes in enantioselectivity of all solvents evaluated. The isoenzymes of PLE were also evaluated and provided very different enantioselective outcomes than that of crude PLE. A series of NMR titrations was performed to explore the interactions between the substrates and ethanol cosolvents.

Improvements to our previously …

Synthesis And Characterization Of Polymer Nanomaterials Using Controlled Radical Polymerization, Lei Wang

Theses and Dissertations

This research focuses on creating and investigating polymer/organic bound interfaces on nanoparticles with advanced architectures to tailor the properties of polymer nanocomposites for various applications. Reversible addition-fragmentation chain transfer (RAFT) polymerization and a toolbox of surface functionalization from the simple to the advanced were developed to prepare the polymer nanomaterials.

In the first part (Chapter 2), a variety of RAFT agents (xanthate, dithiocarbamate and trithiocarbonate) were used to mediate the polymerizations of several classes of free radical polymerizable monomers. These monomers consist of styrene, methyl acrylate, methyl methacrylate, vinyl acetate and isoprene, which have different activities and require different classes …

Photochemical Elimination Reactions That Proceed Via Triplet Excited State Electrocyclic Ring Closures, Himali Devika Jayasekara

Master's Theses (2009 -)

Cage compounds have become an important tool for the study of biological processes. The research focuses on new cage compounds that can unmask functional groups present in biologically important molecules such as proteins, peptides, and oligonucleosides. The project focuses on certain functional groups that are often difficult to release photochemically. These are the thiolate groups present in cysteine residues of proteins and peptides. Thiolate groups are fairly basic leaving groups, unlike the more labile groups such as the carboxylates that are present in proteins and peptides, or the phosphate groups present in nucleosides. The research takes advantage of the ability …

Advancements In The Design, Synthesis, And Application Of Polybenzimidazoles, Alexander Lanier Gulledge

Theses and Dissertations

The overall goal of the work presented within this thesis is to investigate, understand, and develop structure-property relationships in regards to polymer structure, membrane stability, and device performance. Previous work has shown that material properties such as acid loading, proton conductivity, mechanical integrity, and device performance can be attributed to polymer structure, chemical functionality, and polymer architecture (homo, random, co-polymer etc.). Developing and understanding these relationships is critical to the advancement of fuel cell technology. Within this thesis, several of these relationships are investigated and reported.

Novel polymers and copolymer systems have been developed in this research and have significantly …

Design, Synthesis, And Evaluation Of Molecular Inhibitors For Biologically Relevant Enzymes, Sarah Emma St. John

Open Access Dissertations

The work in this thesis details the design, synthesis, and biological evaluation of molecular inhibitors for the inhibition of biologically relevant enzymes. The first three chapters of this thesis concern the polyphenol resveratrol and its inhibition of the quinone reductase 2 (QR2) enzyme. The work on this subject resulted in the complete design, synthesis, biological and structural evaluation of a second generation library of resveratrol analogues. From this work we identified a novel resveratrol analogue that inhibits QR2 in a previously unknown binding orientation. The fourth chapter of this thesis details the de novo design of molecules for the inhibition …

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. …

Design, Synthesis, And Biological Evaluation Of Novel Polyamine Transport System Probes And Their Application To Human Cancers, Aaron Muth

Electronic Theses and Dissertations

The mammalian polyamine transport system (PTS) has been of interest due to its roles in cancer and maintaining cellular homeostasis. Polyamines are essential growth factors which are tightly controlled via a balance of biosynthesis, metabolism, import, and export. This work focused on the development and biological testing of polyamine transport probes to help understand the molecular requirements of the PTS. This was mediated through the use of a CHO (PTS active) and CHO-MG* (PTS deficient) screen, where compounds demonstrating high toxicity in CHO and low toxicity in CHO-MG* were considered PTS selective. The first chapter focused on the development of …

Nmr And Computational Studies Of Nad(P)(H) Cofactor Binding, Junghwa Kim

Master's Theses (2009 -)

Tuberculosis (TB) is one of the most dangerous diseases in a sense of spread method. According W.H.O., one third of world population has this disease and annual one of these infected people spreads 10 -15 people unintentionally. To protect human from this bacterial, the unique feature of mycrobacterial [sic] TB was studied previously. The unique cell wall, peptidoglycan, has high content of DAP (diaminopimelic acid). The disruption of synthesis DAP results in cell death due to instability of cell wall. One way to inhibiting synthesis of DAP is to modify cofactor which acts with dehydrogenase. To do that the study …

Chemical Investigation Of The Antarctic Marine Invertebrates Austrodoris Kerguelenensis & Dendrilla Membranosa And The Antarctic Red Alga Gigartina Skottsbergii, John Alan Maschek

USF Tampa Graduate Theses and Dissertations

The marine realm and, in particular, the Antarctic benthos is largely unexplored and understudied. The chemical investigation reported herein reveals not only the biodiversity, but how that biodiversity manifests remarkable chemical diversity. In our continuing study of the nudibranch Austrodoris kerguelenensis, we have isolated a diverse suite of diterpenoid glyceride esters, palmadorins D - S (2.32 - 2.47), one of which is the first reported halogenated diterpene from a dorid nudibranch. Utilizing genomic data from collaborators, we have investigated the chemical diversity from phylogenetically unique specimens collected in close proximity to one another. Chemical groupings based on comparison of LC/MS …

Chemical Investigation Of The Antarctic Marine Invertebrates Synoicum Adareanum And Artemisina Plumosa, Jaime Heimbegner Noguez

USF Tampa Graduate Theses and Dissertations

Of the small percentage of organisms chemically investigated over the years as potential sources of natural products, much less is known about those from the marine realm. Despite the lack of attention they have received in comparison to terrestrial organisms, marine life have recently been found to represent a valuable source for novel bioactive compounds. Cold water marine habitats are home to a plethora of organisms that have the ability to produce secondary metabolites that exhibit a great deal of diversity in both their chemical structures and biological activities. The chemical investigation of these unique and relatively unstudied ecosystems is …

Pressure Perturbation Calorimetry And Guest-Host Chemistry Of Ndmg And N-Map With P-Sulfonatocalix[6]Arene, Cassandra Newell

Honors Theses

The aim of this project is to provide an explanation for recently obtained binding constants for two similar guest molecules, NDMG and N-MAP, with a p-sulfonatocalix[6]arene host in ammonium acetate buffer. This work was done primarily using pressure perturbation calorimetry, which is a technique that determines the coefficient of thermal expansion, α, which is in turn related to the solute molecule's effect on the order of the surrounding water molecules. A series of experiments were designed to test the effects of suspected confounding variables on the validity of PPC data. PPC was then used to study NDMG and N-MAP in …

Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson

Dissertations and Theses

Pure chromium oxide trifluoride was prepared for the first time by reaction of CrO₃ and ClF with subsequent multiple fluorine treatments at 120°C. On the basis of its infrared spectrum, the purple CrOF₃ was assigned as a fluorine-bridged polymer with terminal oxygen groups. Chromium oxide trifluoride was found to be stable to 300°C, where it decomposes with the loss of oxygen to CrF₃.

Kinetics And Stoichiometry Of The Aquation Reaction Of Pentaaquodihalomethyl Chromium(Iii) Ions, Mohammad Javaid Akhtar

University of the Pacific Theses and Dissertations

This study was designed to provide information about the mechanisms of pentaaquodihalomethyl chromium(III) ions (halo chloro, bromo and iodo).

...

Mechanisms based on carbonium ion, carbeno and carbenoid type intermediates are proposed. A mechanism based on the nucleophillic attack (S_N2) of water on the carbon center leading to a metal-formyl type intermediate is suggested as best fitting all the criteria observed in these studies.

(see PDF file for additional Abstract as it includes formulas)

Trans Diequatorially Fused Blocking Groups For Glucopyranose Derivatives, Basharat Ali Khan

University of the Pacific Theses and Dissertations

No abstract provided.

Cyclic 4,6-Oxygen-Acetal Derivatives Of D-Glucopyrano-(2,3: 4',5')-2'-Oxazolidinones., Daniel Vernie Robinson

University of the Pacific Theses and Dissertations

No abstract provided.

Attempted Synthesis Of 1-Methyl-4-Isopropyl-Hydroxy Bicyclo (3.1.0) Hexane, Kenny Uzoma Acholonu

University of the Pacific Theses and Dissertations

The purpose of this work was to investigate a general synthetic route to 1-Methyl-4-Isopropyl-Hydroxy Bicyclo (3.1.0) Hexane.

3,3-Diphenyl-2-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Allose., Ram Babu

University of the Pacific Theses and Dissertations

A new cyclic protective group has been fused to the cis amino alcohol group of benzyl 2-amino-3,5-o-benzylidene-2-deoxyβ-D-Allopyranoside, by way of a unique rearrangements mechanism. To establish the 2-morpholinone structure, chemical studies, such as reduction and acetylation were conducted.

Comparative spectroscopic studies using ir, pmr, and C-13 nmr confirmed the assigned structures.

The 2-morpholinone ring was cleaved by mild alkaline hydrolysis and could be closed again with acetic anhydride in pyridine. An oxazolidinone derivation of benzyl 2-amino-4,6-o-benzylidene-2-deoxyβ-D-allopyranoside was prepared in a quantitative yield by a modification of a known method.

Protective group properties of the oxazolidinone were studied prior to the …

The Thermal Rearrangement Of Triarylacetonitrile Oxides., Leslie Wayne Gibbs

University of the Pacific Theses and Dissertations

This research is a detailed study of the rearrangement of triarylacetonitrile oxides to the corresponding triarylmethylisocyanates. The kinetics of the rearrangement of triphenylacetonitrlle oxide was followed by infrared absorption spectroscopy using the peak due to the N-0 stretching (1307cm^-1). A study, both, using the differential method (i.e., a plot of the logs of the initial slopes vs. the log of the concentration) and a check of the integrated forms of the rate expressions to determine which gave a constant value for the rate constant showed that the reaction is first order.

From measurements of the rate constant, k, …

Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene, Luther Dickson

University of the Pacific Theses and Dissertations

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently …

Bromination Of 1,2-Cyclononadiene And 1,3-Dimethylallene, Edward Benny Samuel

University of the Pacific Theses and Dissertations

Much information has been obtained on the orientation of unsymmetrical reagents about substituted allenes. Although hydrogen halide addition to 1,2-propadiene yields 2-halopropenes,^20,31 it has been ample demonstrated, at least in the case of halogenation and oxymercuration of the 1,2-alkyl substituted allenes, that the attacking electrophile ends up in the product attached to the central carbon of the original allenic system. ^{20,22,31,34,38,39,40} Using optically active 1,3-dimethylallene(15) it has been shown that the bromination and oxymercuration of 15 is stereospecific. ^22,39Knowledge of the absolute configurations of the optically active addition products have made it possible to propose a plausible mechanism …

Studies Of The Cleavages And Stabilities Of Carbohydrate Epoxides And Epimines, Curtis Alvin Johnson

University of the Pacific Theses and Dissertations

A novel epoxide ring opening of benzyl 3,4-anhydro-2-benzylox-carbonylamido-2-deoxy-β-D-allopyranoside(I) was affected by phenylboronic anhydride in toluene. One of the products was demonstrated to be benzyl 2-benzyloxycarbonylamido-2-deoxy-4,6-0-phenylboronate-β-D-gulopyranoside. Another product isolated, while not identified, had the properties of an anhydro-sugar different from the starting compound(I). Benzyl 6-0-acetyl-2-benzyloxycarbonylamido-2-deoxy-β-D-allopyranoside(II) also underwent epoxide ring opening in a reaction with phenylboronic acid. An isolated product had the properties of a benzyl 2-benzyloxycarbonyiamido-2-deoxy-D-hexoside different from compounds isolate in the reaction of I with the phenyboronate. This indicated the necessity for an unsubstituted 6-OH group in order for the boron compound to be involved in the ring opening. Supporting …

Reactions Of Difunctional Esters With Benzyl 2-Amino-4,6-0- Benzylidene-2-Deoxy-D-Glucopyranosides, Fred Robert Seymour

University of the Pacific Theses and Dissertations

This research is primarily interested in investigating the reactions of benzyl 2-amino-4,6-0-benzylidene-2- deoxy-D-glucopyranoside (I) with various esters. The advantage offered by this sugar is that an alcohol and an amine group are in close proximity, allowing studies of intermolecular vs. intramolecular reactions and observation on anchimeric assistance in intramolecular reactions.

Strained Cycloallenes And Silver Ion Assisted And Unassisted Solvolysis Of Some N,N-Dibromobicyclo(N-3.1.0)Alkanes, Franklin Maurice Boyden

University of the Pacific Theses and Dissertations

The strained cyclic allene intermediates of 1,2-cyclohexadiene, 1,2-cycloheptadiene and 1,2-cyclooctadiene have been successfully generated by the debromination of their corresponding 2,3-dibromocycloalkenes. Evidence for their intermediate existence was obtained by trapping them with the Diels-Alder trapping agent 2,5-diphenyl 1-3,4-benzofuran and by isolating the corresponding addition products.

The goal of this study was to generate the transitory cyclic allenes 1,2-cyclooctadiene, 1,2-cycloheptadiene and 1,2-cyclohexadiene and to investigate some aspects of their chemistry. Evidence for the intermediate existence of these strained cyclic allenes has been found by generating them by the debromination of their corresponding 2,3-dibromocycloalkenes and by trapping the generated cycloallene intermediates with …

A Short Route To Benzyl Beta-D-Glycosides Of 2-Amino-2-Deoxy-D-Glucose And -D-Allose And Elimination Of The 3-Sulfonate From Benzyl 4,6-O-Benzylidene-2-Benzyloxycarbonylamido-2-Deoxy-3-O-(Methylsulfonyl)- Beta-D-Glucopyranoside, William Denham Rhoads

University of the Pacific Theses and Dissertations

It is one purpose of this dissertation to introduce a facile method for the preparation of β glycosides of D-glucose and D-allose.

It is the second purpose of this dissertation to investigate the preparation of 2-oxazolidinones forming a bridge between C₂ and C₃ of allopyranose. This preparation, along with the facile preparation of β-benzyl glycosides of D-glucosamine and D-allosamine, should lead to compounds which, in a few steps, can conceivably be used for coupling at positions 1 and 4.

Cyclic Derivatives Of 2-Amino-2-Deoxy-D-Hexopyranoses, Kenji Miyai

University of the Pacific Theses and Dissertations

The purpose of this investigation was to prepare heterocyclic derivatives, bridging C-2 and C-3 of 2-amino-2-deoxy-D-hexopyranoses, useful as blocking groups in the preparation of aminosugar oligosaccharides and polysaccharides. The work reported herein is concerned with oxazolidones of 2-amino-2-deoxy-D-hexopyranoses (Figure 1).)

There are no examples known, in which five or six-membered rings are fused in a trans-arrangement to five-membered furanose ring. However, although synthetic difficulties were observed, sic and five-membered rings were fused in a trans-arrangement to a sic-membered pyranose ring as pointed out before. In the case of our trans-diequatorially fused oxazolidones additional preparative difficulties were expected, because of the …

A Study Of The Formation Of Cyclic Allenes From 2,3-Dibromocycloalkenes, Michael John Millam

University of the Pacific Theses and Dissertations

This investigation was undertaken in an attempt to form strained cyclic allenes and to study their chemistry. The method chosen for the attempted formation of strained cyclic allenes was the determination of the corresponding 2,3-dibromocycloalkene. 2,3-Dibromocyclononene was synthesized during the course of this investigation so that its debromination to the 1,2-cyclononadiene, which is the smallest stable, 1,2-cycloalkadiene, could be studies as model for the debromination of smaller 2,3-dibromocycloalkenes was initiated. The formation of 1,2-cyclohexadiene was attempted by the debromination of the 2,3-dibromocyclohexene. Evidence for the presence of this unstable intermediate was sought via the use of trapping agents.

Synthesis Of N-Methyl-D-Gulosamine And Methyl Ethers Of N-Methyl-D-Gulosamine, Hazrat Mohammed Noorzad

University of the Pacific Theses and Dissertations

A great variety of amino sugars has been found in antibiotics among these D-gulosamine in the striptomyces group. In the same group, .an N-methylated amino-sugar, N-methyl-L~ glucosamine has been isolated. Although N-methyl-0-gulosamine .has not been found in nature until now, its ultimate discovery would not be surprising in this context. In the present work this amino-sugar and some important derivatives are prepared for the first time, starting from D-glucosamine, a pure benzyl· 3-0-acetyl-2-benzyloxycarbonylamido-2-deoxy-~-D-glucopyranoside (X) was obtained by a series of kno~n processes. Benzyl 3-0-acetyl~-methylsulfonyl-2-deoxy-~-D-glucopyranoside (XIII) and some of its derivatives were obtaine.d from (X). An attempt was made to obtain …

The Synthesis Of Benzyl N-Carbobenzoxy Beta-D-Glucosaminid Uronic Acid Derivatives, Stuart Martin Block

University of the Pacific Theses and Dissertations

The purpose of this research is the preparation and characterization of derivatives of benzyl N-carbobenzoxy-β-D-glucosaminiduronic acid. Previously the derivatives of benzyl N-carbobenzoxy-α-D-glucosaminid-uronic acid have been prepared by H. Weidmann and H. K. Zimmerman (32). The procedure upon which both these uronic acid syntheses is based has been developed with the utilization of platinum in the selective catalytic oxidation of both the benzyl α- and β-D-glucuronosides. The applicability of this research is in the development of new intermediates for the preparation of new diamino sugars or other natural products.

Synthesis Of Benzyl Beta D-Gulopyranosiduronic Acid-(2',3': 4,5)-Oxazolidone-2, Gerald Duane Shryock

University of the Pacific Theses and Dissertations

Although D-glucosamine has been found as a constituent of some antibiotics (28), very little research has been carried out in the area of synthetic preparations. Dutcher (7) recently reviewed the biochemical importance of this class of amino sugars as a constituent of complex antibiotic substances which compose the streptothricin family. For a complete elucidation of these antibiotics, it becomes necessary to investigate thoroughly the synthesis and reactions of the D-glucosamine compounds. Gross et al. (12) have succeeded in preparing the oxazolidone of α-D-glucosamine as well as some derivatives (13) of this compound. The present work reports an attempt to prepare …