Chemistry Commons^™

Design And Synthesis Of Beta-Hairpin Peptidomimetics For Modulating Integrin Mediated Cell Adhesion, Abeta Fibrillogenesis And P53-Mdm2 Protein-Protein Interactions, Priyesh Jain

USF Tampa Graduate Theses and Dissertations

Inhibiting therapeutically important protein-protein interactions has been a tremendous challenge for medicinal chemists. The folded 3D structures of peptides and proteins, mainly comprise secondary structural elements i.e α-helices and β-sheet have created an opportunity to design small molecules and peptidomimetic inhibitors of protein-protein interaction (PPI). Hence, information about the formation and stabilization of these secondary structures is vital for designing future drugs. In this dissertation, several cyclic beta-hairpin peptidomimetics that mimic the recognition surface have been designed and synthesized as inhibitors for different targets such as integrin mediated extracellular matrix -cell adhesion in multiple myeloma, p53-MDM2 PPI, amyloid beta fibrillogenesis …

Corrole Synthesis And Catalytic Applications Toward Cobalt(Iii)-Catalyzed Epoxidation, N-H Insertion, And Cyclopropanation, Chung Sik Kim

USF Tampa Graduate Theses and Dissertations

A variety of bromocorroles, useful precusors for Pd-based cross coupling, were sucessfully synthesized in moderate to good yields. Chiral corroles were also synthesized through use of chiral amides in the aforementioned cross coupling reactions. Cobalt complexes bearing π-acceptor (CNtBu) and σ-donor (PPh3) ligands were also prepared in excellent yields. In this dissertation, cobalt (III) corrole complexes were applied to three different reaction areas: epoxidation, N-H insertion, and cyclopropanation. Cobalt(III) corroles were found to be efficient catalysts for epoxidation reactions. The epoxidation reactions can be carried out using ethyl phenyldiazoacetate, an acceptor/donor diazo compound, as a carbenoid precusor.The reaction provided highly …

Effect Of A Strategically Positioned Methoxy Substituent On The Photochemistry Of 3-Aryl-3h-1-Oxacyclopenta[L]Phenanthren-2-Ones, Roshini Thumpakara, Binoy Jose, Perupparampil Unnikrishnan, Sreedharan Prathapan, Nigam Rath

Chemistry & Biochemistry Faculty Works

Irradiation of 3-methoxy-3-aryl-3H-1-oxacyclopenta[l]phenanthren-2-one derivatives 5a–d resulted in singlet-mediated decarbonylation reaction leading to the formation of phenanthrene derivatives 9a–d. The structure of the photoproduct was unequivocally established on the basis of X-ray crystallographic analysis.

Strategies To Resolve The Three-Dimensional Structure Of The Genome Of Small Single-Stranded Icosahedral Viruses, Eduardo Sanz Garcia

Theses and Dissertations

The aim of this study is the three-dimensional structural characterization of the genome packaging inside viral capsids via cryo-electron microscopy and three-dimensional reconstruction. The genome of some single-stranded viruses can be densely packaged within their capsid shells. Several stretches of the genome are known to adopt stable secondary structures, however, to date, little is known about the three-dimensional organization of the genome inside their capsid shells. Two techniques have been developed to facilitate the structural elucidation of genome packaging: the asymmetric random-model method, and the symmetry-mismatch, random model method. Both techniques were successfully tested with model and experimental data. The …

A Study Of The Vaporization Enthalpies Of Some 1-Substituted Imidazoles And Pyrazoles By Correlation-Gas Chromatography, Dmitry Lipkind, Chatchawat Plienrasri, James S. Chickos

James Chickos

No abstract provided.

The Correlation Of The Concentration Of Selected Metals Determined In Water And Fish Samples From A Public Pond., Paula Kay Edwards

Electronic Theses and Dissertations

The concentrations of heavy metals (Cd, Cu, Fe, Ni, Pb, Zn) were measured in water, and fish samples caught from the pond at Fishery Park in Unicoi County, TN. The water samples were collected once a week for 8 weeks. The amounts of metals in the muscle tissues, gill, and liver of the two fish species were measured. This was to determine if any correlation exists between the metal contents in water and those in the fish samples. The concentration ranges for the heavy metals found in the water samples are as follows: Zn 0.04-0.13; Cu, 0.00-0.00; Pb, 0.00-0.59; Cd, …

Extraction And Determination Of A Selected Polyphenol From Selected Red And Black Grapes By High Performance Liquid Chromatography., Summer Nicole Niles

Undergraduate Honors Theses

Polyphenols are a group of compounds found naturally in plants and they provide much of the flavor, color, and taste to fruits, vegetables, seeds, and other parts of the plants They also act as antioxidants which provide numerous health benefits by protecting cells against damage caused by free radicals. Their antibacterial, anti-inflammatory and anti-allergenic properties have also contributed to the prevention of degenerative diseases, such as cardiovascular diseases and cancers by slowing the rate of oxidative stress on cells. This study was aimed at the identification and quantitation of a specific polyphenol, quercetin, found in grapes commonly purchased at grocery …

Conjugate Additions And Transposition Of The Allylic Alcohols Of Enol Ethers Of 1, 2-Cyclohexanedione., Barnabas Otoo

Electronic Theses and Dissertations

A variety of protected enolic forms of 1, 2-cyclohexanedione was prepared as substrates for conjugate addition studies using organocopper reagents. The sequence involved the enol ether preparation via the enolate, alkylation with an organometalic reagent, and oxidative rearrangement with pyridinium chlorochromate followed by the conjugate addition reactions. Protection of 1, 2-cyclohexanedione was achieved by reacting with chloro tert-butyldimethyl silane and subjected to alkylation. Steric problems were encountered and so an alternative protective group the methoxymethyl acetal was prepared and studied. Alkylation of these derivatives was successful; however, the oxidation was problematic and although evidence for rearrangement was observed in one …

Role Of Amyloid Beta Assembly State In The Human Immune Response, Deepa Viswanathan

Dissertations

Alzheimer’s disease (AD) is a slowly progressing neurodegenerative disease that leads to dementia. Histopathological hallmarks that characterize AD are senile plaques formed by extracellular deposition of Amyloid beta (Aβ) peptide and intracellular aggregates of hyperphosphorylated tau protein. The plaques, which are found in the brain parenchyma, comprise both 40 and 42 residue Aβ. Aggregation of Aβ is an established pathogenic mechanism in AD, but little is known about the initiation of this process in vivo. Several studies have revealed significant inflammatory markers such as activated microglia and cytokines surrounding the plaques. Plaques are a hallmark of AD, but they are …

Retinylidene Iminium Salts And Related Systems, Gary Stephen Shaw

Gary M. Shaw

This thesis encompasses some investigations into the structure and chemistry of iminium salts. The interest in this work stems from previous investigations of the visual pigment rhodopsin and a related protein, bacteriorhodopsin. Both of these proteins have been shown to consist of an iminium salt linkage between the chromophore and the protein. Also, these compounds are able to absorb light in the visible region of the spectrum and undergo efficient isomerization processes. A series of iminium salts related to these natural chromophores were prepared and characterized by a variety of spectroscopic methods in both solution and the solid states. In …

Sequence-Specific And Conformation-Specific Targeting Of Duplex And Quadruplex Dna Grooves With Small Molecules, Rupesh K. Nanjunda

Chemistry Dissertations

Small molecule mediated chemical intervention of biological processes using nucleic acid targets has proven extremely successful and is continually providing exciting new avenues for the development of anti-cancer agents and molecular probes. Among the alternative DNA confrormations, G-quadruplexes has certainly garnered much recognition due to increase in evidences supporting their involvement in diverse biological process. The grooves of the quadruplexes offer an alternate recognition site for ligand interactions with potentially higher selectivity than the traditional terminal stacking sites. DB832, a bifuryl-phenyl diamidine, was recently reported to selectively recognize human telomeric G-quadruplex, as a stacked species, with significant selectivity over duplex …

The Vinylguaiacol/Indole Or Vgi ("Veggie") Ratio: A Novel Molecular Parameter To Evaluate The Relative Contributions Of Terrestrial And Aquatic Organic Matter To Sediments., Michael A. Kruge, Kevin K. Olsen, Jaroslaw W. Slusarczyk, Elaine Gomez

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The organic matter (OM) fraction of estuarine sediments is often distinctive and thus diagnostically useful in determinations of sedimentary provenance. Among the most fundamental distinctions to be made is that between terrestrial and aquatic OM. To supplement the parameters commonly used for this purpose (e.g., C/N and stable isotope ratios), we proposed the Vinylguaiacol/Indole or VGI ("Veggie") ratio, defined as [vinylguaiacol / (indole + vinylguaiacol)] using data produced by analytical pyrolysis-gas chromatography/mass spectrometry of dried, homogenized sediment samples. The ratio employs the peak areas of these two compounds on the mass chromatograms of their molecular ions (m/z 150 and 117). …

Chemical Vapor Deposition Of Silanes And Patterning On Silicon, Feng Zhang

Theses and Dissertations

Self assembled monolayers (SAMs) are widely used for surface modification. Alkylsilane monolayers are one of the most widely deposited and studied SAMs. My work focuses on the preparation, patterning, and application of alkysilane monolayers. 3-aminopropyltriethoxysilane (APTES) is one of the most popular silanes used to make active surfaces for surface modification. To possibly improve the surface physical properties and increase options for processing this material, I prepared and studied a series of amino silane surfaces on silicon/silicon dioxide from APTES and two other related silanes by chemical vapor deposition (CVD). I also explored CVD of 3-mercaptopropyltrimethoxysilane on silicon and quartz. …

Biomarkers Of Mild Cognitive Impairment And Alzheimer's Disease, Mark A. Lovell, Bert C. Lynn

Chemistry Faculty Patents

A method for quantifying a neurodegenerative disorder in a patient that includes obtaining a fluid sample from the subject; measuring a protein biomarker complex in said fluid sample and correlating the measurement with mild cognitive impairment or Alzheimer's disease status. The biomarkers include those that comprise at least one of a transthyretin protein and/or a prostaglandin-H2 D-isomerase protein, and at least one second, different protein selected from a transthyretin, prostaglandin-H2 D-isomerase, beta-2-microglobulin, cystatin C, superoxide dismutase [Cu—Zn], plasma retinol-binding protein, phosphatidylethanolamine-binding protein, carbonic anhydrase 2, prostaglandin-H2 D-isomerase, and/or serotransferrin protein.

Precatalysts Useful In Polyolefin Polymerization Reactions, Omofolami Tesileem Ladipo, Richard Eaves, Alexey Zazybin, Sean Parkin

Chemistry Faculty Patents

Compounds are provided that are useful as precatlysts in the polymerization of olefins such as ethylene and propylene. Other compounds are useful as intermediates in the production of such precatalysts.

Superhydrophobic Thin Films Fabricated By Reactive Layer-By-Layer Assembly Of Azlactone-Functionalized Polymers, Maren E. Buck, Sarina C. Schwartz, David M. Lynn

Chemistry: Faculty Publications

We report an approach to the fabrication of superhydrophobic thin films that is based on the "reactive" layer-by-layer assembly of azlactone-containing polymer multilayers. We demonstrate that films fabricated from alternating layers of the azlactone functionalized polymer poly(2-vinyl- 4,4-dimethylazlactone) (PVDMA) and poly(ethyleneimine) (PEI) exhibit micro- and nanoscale surface features that result in water contact angles in excess of 150°. Our results reveal that the formation of these surface features is (i) dependent upon film thickness (i.e., the number of layers of PEI and PVDMA deposited) and (ii) that it is influenced strongly by the presence (or absence) of cyclic azlactone-functionalized oligomers …

Isomer-Dependent Adsorption And Release Of Cis- And Trans-Platin Anticancer Drugs By Mesopomus Silica Nanoparticles, Zhimin Tao, Youwei Xie, Jerry Goodisman, Tewodros Asefa

Chemistry - All Scholarship

We report on adsorption and release of the anticancer drugs cisplatin and transplatin from mesoporous silica nanomaterials, emphasizing the differences between cisplatin and its much less toxic isomer. Two types of particles, M.CM-41 and SBA-IS, were used, either as just synthesized or after calcination to remove the templates. The particles were characterized by TEM, nitrogen physisorption, and elemental analysis. The UV-vis spectra of cisplatin and transplatin were obtained and the intensities of several bands (205-210 nm, 210-220 nm, 220-235 nm, and 300-330 nm) were found proportional to drug concentrations, allowing their use for measuring drug concentration. To evaluate drug adsorption …

Activation Of Propargylic Alcohols By Piano-Stool Ruthenium Complexes Bearing Phosphoramidite Ligands, Stephen Andrew Costin

Dissertations

Various piano-stool ruthenium complexes bearing phosphoramidite ligands have been synthesized and characterized spectroscopically and in some cases structurally. Reaction of phosphoramidite ligands with an appropriate metal precursor gives new piano-stool ruthenium complexes [RuCl(L)(arene)(phosphoramidite)], where L = Cl, PPh3, or others. The novel complexes are tested for their ability to activate propargylic alcohols catalytically as well as stoichiometrically. Specifically, catalytic substitution of propargylic alcohols via allenylidene intermediates is envisioned. Stoichiometric reactions designed to form stable, isolable allenylidenes are sought as well. h6-p-cymene complexes of the type [RuCl2(h6-p-cymene)(phosphoramidite)] activate propargylic alcohols in the reaction with carboxylic acids to form b-oxo esters. The …

10th Annual Senior Research Symposium Of The Department Of Biological Sciences, Chemistry And Biochemistry, Messiah College

School of Science, Engineering & Health (SEH) Symposium

No abstract provided.

Ua1b1/2 L.Y. Lancaster Lecture Series, Wku Archives

WKU Archives Collection Inventories

Records regarding the L.Y. Lancaster Lecture Series.

Hybrid Micro-/Nanogels For Optical Sensing And Intracellular Imaging, Weitai Wu, Shuiqin Zhou

Publications and Research

Hybrid micro-/nanogels are playing an increasing important part in a diverse range of applications, due to their tunable dimensions, large surface area, stable interior network structure, and a very short response time. We review recent advances and challenges in the developments of hybrid micro-/nanogels toward applications for optical sensing of pH, temperature, glucose, ions, and other species as well as for intracellular imaging. Due to their unique advantages, hybrid micro-/nanogels as optical probes are attracting substantial interests for continuous monitoring of chemical parameters in complex samples such as blood and bioreactor fluids, in chemical research and industry, and in food …

Direct Patterning Of Silanized-Biomolecules On Semiconductor Surfaces, Dorjderem Nyamjav, Richard C. Holz

Chemistry Faculty Research and Publications

A novel approach to pattern silanized-biomolecules directly onto glass (SiO_x) substrates via Dip-Pen nanolithography (DPN) and microcontact printing (μCP) is presented. Subsequent hybridization reactions of DPN patterned silanized-DNA with its complementary strands provide “proof-of-concept” that the patterned oligonucleotides maintain their biological activities. The fabrication strategy does not require premodification of substrates and offers a cheap and robust way to immobilize molecules on electronically important semiconductor surfaces.

Dual Inhibition Of Sodium-Mediated Proton And Calcium Efflux Triggers Non-Apoptotic Cell Death In Malignant Gliomas, William Harley, Candace Floyd, Tamara Dunn, Xiao-Dong Zhang, Tsung-Yu Chen, Manu Hegde, Hasan Palandoken, Michael H. Nantz, Leonardo Leon, K.L. Carraway Iii, Bruce Lyeth, Fredric A. Gorin

Chemistry and Biochemistry

Malignant glioma cells maintain an elevated intracellular pH (pH_i) within hypoxic–ischemic tumormicroenvironments through persistent activation of sodium–proton transport (McLean et al., 2000). Amiloride has been reported to selectively kill human malignant glioma cell lines but not primary astrocytes (Hegde et al., 2004). While amiloride reduces pH_i of malignant gliomas by inhibiting isoform 1 of sodium–proton exchange (NHE1), direct acidification was shown to be cytostatic rather than cytotoxic. At cytotoxic concentrations, amiloride has multiple drug targets including inhibition of NHE1 and sodium–calciumexchange. Amiloride's glioma cytotoxicity can be explained, at least in part, by dual inhibition of NHE1 and …

Nicholas Reactions In The Construction Of Cyclohepta[De]Naphthalenes And Cyclohepta[De]Naphthalenones. The Total Synthesis Of Microstegiol, Rafiq Taj, James R. Green

Chemistry and Biochemistry Publications

The application of the Nicholas reaction chemistry of 2,7-dioxygenated naphthalenes in the synthesis of cyclohepta[de]napthalenes and in the synthesis of (±)-microstegiol (1) is presented. The substitution profile of Nicholas monosubstitution (predominantly C-1) and disubstitution reactions (predominantly 1,6-) on 2,7-dioxygenated napthalenes is reported. Application of a 1,8-dicondensation product and selected C-1 monocondensation products to the construction of cyclohepta[de]naphthalenes by way of ring closing metathesis and intramolecular Friedel−Crafts reactions, respectively, is described. Deprotection of the C-7 oxygen function to the corresponding naphthol allows tautomerization to cyclohepta[de]naphthalene-1-ones upon seven-membered-ring closure in most cases, and replacement …

Intramolecular Nicholas Reactions In The Synthesis Of Dibenzocycloheptanes. Synthesis Of Allocolchicine Nsc 51046 And Analogues And The Formal Synthesis Of (−)-Allocolchicine, Sinisa Djurdjevic, Fei Yang, James R. Green

Chemistry and Biochemistry Publications

The preparation of dibenzocycloheptyne-Co₂(CO)₆ complexes by intramolecular Nicholas reactions of biaryl-2-propargyl alcohol-Co₂(CO)₆ derivatives is described. Reductive decomplexation of the dibenzocycloheptyne-Co₂(CO)₆ complexes affords the corresponding dibenzocycloheptenes, individual members of which have been employed in a formal total synthesis of (−)-allocolchicine, the preparation of 6,7-dihydro-3,4,9,10,11-pentamethoxy-5H-dibenzo[a,c]cyclohepten-5-one, and the enantioselective total syntheses of NSC 51046 and its 3,8,9,10-tetramethoxy regioisomer.

Measurements Of Gas‐Phase Inorganic And Organic Acids From Biomass Fires By Negative‐Ion Proton‐Transfer Chemical‐Ionization Mass Spectrometry, P. Veres, James M. Roberts, I. R. Burling, C. Warneke, Joost De Gouw, Robert J. Yokelson

Chemistry and Biochemistry Faculty Publications

[1] Emissions from 34 laboratory biomass fires were investigated at the combustion facility of the U.S. Department of Agriculture Fire Sciences Laboratory in Missoula, Montana. Gas-phase organic and inorganic acids were quantified using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), open-path Fourier transform infrared spectroscopy (OP-FTIR), and proton-transfer-reaction mass spectrometry (PTR-MS). NI-PT-CIMS is a novel technique that measures the mass-to-charge ratio (m/z) of ions generated from reactions of acetate (CH₃C(O)O⁻) ions with inorganic and organic acids. The emission ratios for various important reactive acids with respect to CO were determined. Emission ratios for isocyanic acid (HNCO), 1,2 …

Novel Electrochemical Detections Of Biologically And Environmentally Relevant Substances, Clarissa E. Tatum

Doctoral Dissertations

Development and studies of new electrochemical methods for the detection of various biologically and environmentally relevant substances are the focus of this dissertation. A dual amperometric sensor, capable of the simultaneous, real-time determination of NO and O,2, has been developed and optimized. Many tests were performed in order to reduce cross-talking between the two sensors, and an electro-deposited polymer, poly-5-amino-1-naphthol, was shown to reduce the cross-talking to insignificant levels. The use of bismuth-based electrodes in the detection of various metals has been explored. A bismuth bulk electrode has been developed, optimized, and used for the individual and simultaneous determination of …

Tantalum Carbene And Imide Complexes. Synthesis, Characterization, And Pathways Of Formation, Julia Kathryn Covington Abbott

Doctoral Dissertations

This dissertation focuses on two different types of organometallic compounds, carbenes and imides. The first project deals with the archetypal Schrock carbene, and the second project studies complexes that contain metal-nitrogen bonds, both amides and imides.

A summary of the research in this dissertation is discussed in Chapter 1. Chapter 2 begins the studies of the archetypal Schrock carbene (Bu^tCH₂)₃Ta=CHBu^t. The studies include the synthesis of deuterated compounds (Bu^tCD₂)₃TaCl₂ and Bu^tCD₂Li, observation and identification of the intermediate, Ta(CD₂Bu^{t …}

The Importance Of Chain Connectivity In The Formation Of Non-Covalent Interactions Between Polymers And Single-Walled Carbon Nanotubes And Its Impact On Dispersion, Dias Linton

Doctoral Dissertations

Polymer nanocomposites have garnered incredible promise in the field of material science due to the excellent mechanical strength, thermal and electrical conductivities of the nanoparticles and the extension of these properties to the processing flexibility inherent to plastics. However, practical realization of these nanoparticle-based materials has been hindered by the tendency of these nanoparticles to aggregate as a result of strong inter-particle forces. In this dissertation, we investigate the formation of non-covalent charge transfer interactions between polymers and single-walled carbon nanotubes (SWNTs) with the goal of optimizing interfacial adhesion and homogeneity of nanocomposites without modifying the SWNT native surface.

Nanocomposites …

On The Perfection Of Broccoli: Talking To Ed Brush, Lee Torda

Bridgewater Review

No abstract provided.