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Chemical, Biological, And Preliminary In Vitro Studies Of Novel Vanadium(Iv) Complexes With Schiff Bases And Thiosemicarbazone Ligands, Nerissa Abigail Lewis

Master's Theses

9-Anthraldehyde-N(4)-methylthiosemicarbazone (MeATSC), potassium (E)-2-(2-hydroxybenzylideneamino)-3-(1H-indol-3-yl)propanoate (K[(Sal-L-tryp)] and 2-(2-hydroxybenzylamino)-3-(1H-indol-3-yl)propanoic acid (the reduced Schiff base) were prepared using known synthetic procedures. Two novel thiosemicarbazone ligands, (E)-N-ethyl-2-(4-hydroxy-3-methoxybenzylidene)hydrazinecarbothioamide (N-Ethhymethohcarbthio) and (E)-N-ethyl-2-(1-(thiazol-2-yl)ethylidene)hydrazinecarbothioamide (acetylethTSC), were also prepared. All ligands were characterized by FT IR and electrochemistry. N-Ethhymethohcarbthio were characterized by elemental analysis whereas the reduced Schiff base and K[(Sal-L-tryp)] were characterized by ESI MS. X-ray crystallography was also used to characterize acetylethTSC. The ligands were then reacted with [VO(Sal-L-tryp)(H2O)] (1) (Sal-L-tryp = N-salicylidene-L-tryptophanate) to produce the …

Fabrication And Selective Functionalization Of Amine-Reactive Polymer Multilayers On Topographically Patterned Microwell Cell Culture Arrays, Adam H. Broderick, Samira M. Azarin, Maren E. Buck, Sean P. Palecek, David M. Lynn

Chemistry: Faculty Publications

We report an approach to the fabrication and selective functionalization of amine-reactive polymer multilayers on the surfaces of 3-D polyurethane-based microwell cell culture arrays. "Reactive" layer-by-layer assembly of multilayers using branched polyethyleneimine (BPEI) and the azlactone- functionalized polymer poly(2-vinyl-4,4′-dimethylazlactone) (PVDMA) yielded film-coated microwell arrays that could be chemically functionalized postfabrication by treatment with different amine-functionalized macromolecules or small molecule primary amines. Treatment of film-coated arrays with the small molecule amine d-glucamine resulted in microwell surfaces that resisted the adhesion and proliferation of mammalian fibroblast cells in vitro. These and other experiments demonstrated that it was possible to functionalize different structural …

Microfluidic Paper-Based Analytical Devices: From Pocket To Paper-Based Elisa, Andres W. Martinez

Chemistry and Biochemistry

Microfluidic paper-based analytical devices (microPADs) began as a simple idea with an ambitious goal. The idea was to make microfluidic devices out of paper instead of plastic or glass. The goal was to develop low-cost and portable paper-based diagnostic devices to improve healthcare in developing countries. Over the past 6 years, many developments have been made in the emerging field of paper-based microfluidic devices. Reviewing the development of these devices in the Whitesides group at Harvard University (Cambridge, MA, USA) can provide some insight into the future of the field and encourage scientists from a variety of backgrounds to contribute …

Constituents Of Plantago Major Subsp. Intermedia With Antioxidant And Anticholinesterase Capacities, Ufuk Kolak, Mehmet Boğa, Emi̇ne Akalin Uruşak, Ayhan Ulubelen

Turkish Journal of Chemistry

The methanol extract of Plantago major subsp. intermedia (Gilib.) Lange afforded 4 known compounds, namely isomartynoside (1), 10-hydroxymajoroside (2), \beta -sitosterol (3), and ursolic acid (4). Their structures were established by spectroscopic methods. After determination of the total phenolic and flavonoid contents of the methanol extract, the antioxidant potentials of the crude extract and isolated compounds 1-4 were determined by \beta -carotene bleaching, DPPH free radical and ABTS cation radical scavenging, and cupric reducing antioxidant capacity methods. The methanol extract, rich in phenolic contents, indicated the same DPPH free radical scavenging activity (72\% inhibition) as a standard compound, butylated hydroxytoluene, …

Single Cell Analysis For The Characterization Of Cell Populations Using A Live Cell Array, Maureen Ann Walling

Legacy Theses & Dissertations (2009 - 2024)

In the past decade, the shift from whole cell population analyses towards single cell measurement methods and techniques is based on experimental results that reveal significant levels of non-genetic heterogeneity in clonal cell populations. This heterogeneity manifests in multiple aspects of cell activity and is, in part, a result of stochastic noise in processes leading to gene expression, namely transcription and translation. The growing understanding of this occurrence has led to the development of methods to monitor and analyze heterogeneity for a more thorough description of cell populations and overall activity.

Preparation And Studies Of Ratiometric Fluorescent Chemosensors Based On The Attenuation Of Excitation Energy Transfer, Jiba Raj Acharya

LSU Doctoral Dissertations

Molecular devices possessing pi-electron conjugated scaffold demonstrate unique capabilities as fluorescent chemosensors for the trace detection of analytes in a variety of environments. Important properties of these compounds such as charge transport and exciton migration, emission intensity etc. can be simply attenuated by external stimuli or analyte binding, leading to considerable changes in observable signals. The main goal of this Ph.D. dissertation was to study the possibility to control excitation energy migration in conjugated systems. Towards this goal, we designed surface-immobilized monodispersed oligo(p-phenylene ethynylene)s (OPEs) as a general basis for thin-film ratiometric fluorescent chemosensors. The sensor molecules have been functionalized …

Synthesis, Biological And Photophysical Studies Of Novel Compounds For Cancer Therapy, Edith Khavwajira Amuhaya

LSU Doctoral Dissertations

Cancer remains the second most common cause of death in the United States. It is therefore imperative that a lot of effort be put into finding a cure for this dreadful disease that shows no discrimination, and virtually anybody is at risk of developing the disease. Chapter 1 introduces basic facts about cancer and the available treatments, including PDT and BNCT. Our focus will be on these two bimodal therapies, which form the basis of my research work, which involves the synthesis of potential sensitizers to be used either in PDT or BNCT or both. In Chapter 2, I discuss …

Formation And Stabilization Of Combustion-Generated Environmentally Persistent Free Radicals On Transition Metal Oxides Supported On Silica, Eric Warren Pimentel Vejerano

LSU Doctoral Dissertations

The formation of environmentally persistent free radicals in combustion system was investigated from chemisorptions of chlorine- and hydroxy-substituted benzenes on transition metal oxide surface under post-combustion conditions. This manuscript reports the formation of EPFRs on silica particles containing 5% Fe(III)2O3, Ni(II)O, and Zn(II)O. The EPFRs are formed by the chemisorption of substituted aromatic molecular adsorbates on the metal cation center followed by electron transfer from the adsorbate to the metal ion at temperatures from 150 to 400 oC. Depending on the nature of the adsorbate and the temperature, two organic EPFRs were formed: a phenoxyl-type radical, which has a lower …

The Synthesis, Characterization, And Electrochemical Study Of Tris(Pyrazolyl)-Type Iron(Ii) Complexes, Iron(Ii) Sulfur- And Selenium-Containing Complexes, And Tris(Pyrazolyl)-Type Ruthenium(Ii) Complexes, Christopher Underwood

All Theses

Highly reactive radical species such as hydroxyl radical cause oxidative stress, resulting in chronic or degenerative diseases. In the biological Fenton reaction, iron(II) generates hydroxyl radical, OH, but only within a specific electrochemical potential window (-324 mV to 640 mV). Selenium and sulfur compounds have been extensively studied for their antioxidant properties, and they may exert their effects by binding iron(II) and shifting its electrochemical potential out of this window. This work has investigated the synthesis and electrochemical characterization of iron(II) chalcogenate complexes and iron(II) chalcogenone complexes. Cyclic voltammetry (CV) of [Fe(EPh)4][(PPh4)2] (E = S, Se) complexes shows Fe2+/3+ redox …

The Design And Synthesis Of Functionalized Porphyrins And Their Applications In Group Transfer Reactions, Medicine, And Materials, Kimberly Bliss Fields

USF Tampa Graduate Theses and Dissertations

Porphyrins and their analogs are a class of chemically and biologically important compounds that have found a variety of applications in different fields such as catalysis, medicine, and materials. The physical, chemical, and biological dependence of the peripheral substituents of porphyrins on their properties has prompted great effort towards the synthesis of new porphyrins with different electronic, steric, and conformational environments. To this end, porphyrins have been prepared using a modular approach from bromo- and triflate synthons. These synthons underwent palladium-catalyzed cross-coupling with chiral amines, amides, alcohols, and boronic esters to create products that were tested for biological activity.

Metalloporphyrins …

Chemical Characterization Of Botanical Products: Comprehensive Speciation By Liquid Chromatography Particle Beam Mass Spectrometry, Joaudimir Castro Georgi

All Dissertations

The dietary supplement industry has expanded and many of these supplements have become an important aspect of people's everyday lives. In 1994, the U.S. Dietary Supplement Health and Education Act (DSHEA) classified numerous nutraceutical/botanical products as dietary supplements because of their beneficial medicinal properties and provided the necessary regulation to the supplement producers. Since then, the interest of the scientific community towards dietary supplements has grown intensively and numerous studies have been carried out in order to understand the chemical behavior of the active molecules in the human body. The development towards analytical methods for the quantification of the active …

Characterization Of Plutonium Particles Originating From The Bomarc Accident -1960, Richard Charles Gostic

UNLV Theses, Dissertations, Professional Papers, and Capstones

Within the U.S. arsenal, 32 accidents with nuclear weapons were reported between 1950 and 1980. One of these accidents occurred at McGuire AFB in 1960. A BOMARC missile armed with a nuclear warhead caught on fire and as a result the warhead was destroyed. Sub-millimeter particles consisting of weapons grade plutonium (WGPu) produced by this accident were distributed around the site and remained in the environment for 47 years. Soil cores known to contain WGPu particles produced by this accident were obtained. The particles were localized and removed from the soil with the aid of high resolution computed tomography. The …

The Development Of An Effective Water-Soluble Receptor For Pyrene Derivative Dyes, Ashley Longstreet

Undergraduate Theses and Capstone Projects

A receptor with enhanced water solubility was synthesized from an existing receptor to be used as a pyranine fluorescence quencher in endovesiculation detection assays. The existing receptor consisted of a cyclen core with four protruding arms containing an aryl nitro group at each end. Its poor water solubility limited the accuracy and precision of the endovesiculation assay because the low concentration of receptor did not match the concentration of pyranine. To increase the water solubility, ethoxy groups were attached to the ends of each arm by first selectively reducing the nitro group to an amine with NaBHU4, H2, and a …

Characterization Of Phytochemicals Isolated From Plants Of The Pacific Northwest And Western United States For Combating Fungal Multidrug Resistance, John David Schreiber

Undergraduate Honors Theses

Fungal multidrug resistance is an emerging problem for those suffering from fungal infections, and for those seeking to discover or produce novel fungicidal drugs. Plants native to the Pacific Northwest as well as in the Olympic national rainforest were collected and screened for phytochemicals which exhibit direct antifungal activity toward Candida and Saccharomyces spp. as well as those that inhibit fungal ABC transporters that are, in large part, responsible for the development of multidrug resistance. Dalea formosa (Fabaceae), a plant native to the American Southwest, was also screened for phytochemicals of medicinal interest. The methanolic extract of aerial portions of …

Synthesis Of Functionalized Gpi Anchors And Related Glycoconjugates, Benjamin M. Swarts

Wayne State University Dissertations

This dissertation is divided into two chapters describing the background, significance, and synthesis of GPI anchors and GPI-anchored molecules. GPI anchors are a class of complex glycolipids with the primary purpose of attaching cell surface proteins/glycoproteins to the cell membrane. The first chapter is focused on the synthesis of functionalized GPI anchors, and begins with an introductory look at the discovery, structure, biosynthesis, and biological functions of GPIs. Then, after surveying progress and achievements in GPI synthesis, including discussion about current strategic shortcomings in the field that prevent the chemical synthesis of various GPI derivatives, our approach to accessing uniquely …

Elucidating The Structure Of Protein Aggregates By Raman Spectroscopy, Ludmila A. Popova

Legacy Theses & Dissertations (2009 - 2024)

The structures and properties of amyloid fibrils are of considerable interest due to their associations with numerous neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease and transmissible spongiform encephalopaties (prion diseases). Understanding fibrillogenesis at a molecular level requires detailed structural characterization of amyloid fibrils. However amyloid fibrils are difficult objects to study due to their non-crystalline and insoluble nature. These properties make the application of classical tools of structural biology, such as X-Ray crystallography and solution Nuclear Magnetic Resonance spectroscopy, impractical for structural characterization of protein fibrils.

Some Bioactive Organotin(Iv) Derivatives With 3,4-Dichlorophenylacetic Acid: Synthesis, Spectroscopic Properties, And X-Ray Structure Of [Sn_4(C_4h_9)_8(Oocch_2c_6h_3cl_2)_4o_2], Muhammad Adeel Saeed, Muhammad Khawar Rauf, . Imtiaz-Ud-Din, Amin Badshah, Muhammad Zaeem Akhtar, Bushra Mirza

Turkish Journal of Chemistry

Some bioactive organotin(IV) derivatives of 3,4-dichlorophenylacetic acid (HL) were synthesized by reacting the ligand acid with various di- or tri-organotin compounds (in suitable mole ratios) in the presence of triethylamine. The structural investigation was carried out via multinuclear (^1H, ^{13}C, and ^{119}Sn) NMR, IR spectroscopy, and X-ray crystallography. The crystal structure of 4 comprises a central Sn_2O_2 core with O atoms bonded to 2 dibutylbis(3,4-dichlorophenylacetato)tin(IV) units. All the Sn atoms of 4 are essentially 5-coordinated in distorted trigonal-bipyramidal geometry. Some of the compounds exhibited significant antibacterial and antifungal activity.

Synthesis, Characterization And Biological Activity Of Copper (Ii) And Zinc (Ii) Complexes Of Thiosemicarbazones And Their N(4)-Substituted Derivatives Derived From 2,4-Dihydroxybenzaldehyde., Tan Kong Wai

Student Works (2010-2019)

Four thiosemicarbazones ligands (1-4) have been prepared with good yield by refluxing 2,4-dihydroxybenzaldehyde with thiosemicarbazide or N(4)-substituted thiosemicarbazide in ethanol or methanol. From these four ligands, 16 new ternary metal complexes (5-20) with the general formulation of M(B)L have been prepared from the reactions of metal acetates with 2,4-dihydroxybenzaldehyde N(4)-substituted thiosemicarbazone in the presence of N,N-heterocyclic base (M2+ = Zn2+ or Cu2+; B = 2,2'-bipyridine, (bpy); 1,10-phenanthroline, (phen); L2- = doubly deprotonated thiosemicarbazones = 2,4-dihydroxybenzaldehyde thiosemicarbazonato, (HT); 2,4-dihydroxybenzaldehyde 4-methylthiosemicarbazonato, (HM); 2,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazonato, (HE) and 2,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazonato, (HP)) These compounds have been characterized by elemental analyses, IR, UV-Vis, NMR and magnetic …

Skeletal Pathology Of Tibiotarsi In Chick Embryos Exposed To Platinum Group Metals By Micro-Raman Spectroscopy, Jennifer L. Monahan

Browse all Theses and Dissertations

Platinum group metals (PGMs) have been shown to accumulate in various tissues of organisms but their toxicity is not well-known. Raman spectroscopy is a powerful analytical technique that enables direct and non-destructive chemical characterization of bone tissues. PGMs were injected into chick embryos in the following concentrations: 0.1, 1.0, 5.0, or 10.0 ppm solutions of Pt^(IV), Rh^(III), Pd^(II) or PGMs mixtures (0.1 ppm or 1.0 ppm of each metal). The micro-Raman maps recorded on the paraffin embedded tibiotarsus cross-sections showed significant changes in the chemical composition and structure of the bone tissue as a result …

Chemistry Of Rhenium(I) Tricarbonyl Complexes Of Biomedical Relevance, Theshini Perera

LSU Doctoral Dissertations

fac-[Re^I(CO)₃L]ⁿ complexes serve as models for short-lived fac-[^99mTc^I(CO)₃L] imaging tracers. Dangling groups on L, needed to achieve desirable biodistribution, complicate the NMR spectra, which are not readily understood. In fac-[Re^I(CO)₃L]⁺ with less complicated L, NH groups (exo-NH) projecting toward the L face sometimes showed an upfield shift attributable to steric shielding of the exo-NH group from the solvent by the chelate rings. To investigate whether exo-NH groups in six-membered rings exhibit the same effect and whether the …

Synthesis And Conjugation Of Terminal Α-Galactose Containing, Roger Allan Ashmus

Open Access Theses & Dissertations

Over 16 million people in Latin America are infected with the protozoan parasite Trypanosoma cruzi (T. cruzi), the causative agent of Chagas disease, and up to 50,000 infected people die annually due to complications during the chronic stage of the disease. To date, there are no vaccines or effective drugs to treat chronic Chagas disease. It is known that T. cruzi contains cell surface mucin-like glycoproteins with terminal α-galactosyl residues, and it is well established that they are highly immunogenic. The exact structure of the immunogenic carbohydrate epitopes, however, remains unknown. To determine which epitopes have the ability to interact …

Development Of A Fluorescent Probe For Determination Of Water Transport In Subcellular Organelles, Adriana Chaurra-Arboleda

All Dissertations

Water transport has been widely studied in a variety of cells and isolated membranes. However, the intrinsic complexity related with the study of intracellular processes has delayed the development of an analytical technique for the study of water transport in subcellular compartments of living cells. This study represents the development and application of a ratiometric fluorescent probe to study water transport in endocytic organelles of intact living cells. The probe is based on the use of a D₂O-sensitive fluorophore, Lucifer yellow dextran (LY-dex), together with a D₂O-insensitive fluorophore, Alexa fluor 546 dextran (AF546-dex), used as an …

Chemical Modification Of Reactive Multilayered Films Fabricated From Poly(2-Alkenyl Azlactone)S: Design Of Surfaces That Prevent Or Promote Mammalian Cell Adhesion And Bacterial Biofilm Growth, Maren E. Buck, Anthony S. Breitbach, Sonja K. Belgrade, Helen E. Blackwell, David M. Lynn

Chemistry: Faculty Publications

We report an approach to the design of reactive polymer films that can be functionalized post-fabrication to either prevent or promote the attachment and growth of cells. Our approach is based on the reactive layer-bylayer assembly of covalently crosslinked thin films using a synthetic polyamine and a polymer containing reactive azlactone functionality. Our results demonstrate (i) that the residual azlactone functionality in these films can be exploited to immobilize amine-functionalized chemical motifs similar to those that promote or prevent cell and protein adhesion when assembled as self-assembled monolayers on gold-coated surfaces and (ii) that the immobilization of these motifs changes …

Sonication Assisted Synthesis Of Oligomannosides, Christabel Tomla Tanifum

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Oligomannosides prevalently exist as cell surface antigens. They play important roles in diseases such as viral infection and cancer, and they have been shown to be useful as candidates for vaccines. HIV, one of the most devastating modern diseases, has a high content of mannose sugars on its envelope glycoprotein gp120. Oligomannosides of the HIV virus, also called Man9, which are found on the glycoprotein gp120, have been shown to play a protective role for the HIV virus, shielding highly conserved protein domains of gp120 from proteolytic attacks. Thus gp120 plays an important role in HIV infection of cells, being …

Isolation And Characterization Of Aromatase Inhibitors From Brassaiopsis Glomerulata (Araliaceae), Marcy J. Balunas, Bin Su, Soedarsono Riswan, Harry H.S. Fong, Robert W. Brueggemeier, John M. Pezzuto, A. Douglas Kinghorn

Chemistry Faculty Publications

The hexane- and ethyl acetate-soluble extracts of the leaves of Brassaiopsis glomerulata (Blume) Regel (Araliaceae), collected in Indonesia, were found to inhibit aromatase, the rate-limiting enzyme in the production of estrogens from androgens, in both enzyme- and cell-based aromatase inhibition (AI) assays. Bioassay-guided fractionation led to the isolation of six known compounds of the steroid and triterpenoid classes (1–6) from the hexane extract, of which 6β-hydroxystimasta-4-en-3-one (5), was moderately active in the cell-based AI assay. Fractionation of the ethyl acetate extract afforded seven pure isolates (7–13) of the modified peptide, fatty acid, monoterpenoid, and benzenoid types, including six known compounds …

Design, Synthesis, And Characterization Of Novel Hydrophilic Fluorene-Based Derivatives For Bioimaging Applications, Dao Nguyen

Electronic Theses and Dissertations

In this work, hydrophilic fluorene-based derivatives that contain ethylene oxide substituents, have been synthesized and characterized for potential use as new fluorophores for bioimaging applications and for fluorescence sensing of heavy metals. Symmetrical and unsymmetrical fluorene derivatives based on structural types of acceptor-pi-acceptor, acceptor-pi-donor, and donor-pi-donor were characterized by TGA, UV-vis absorption, fluorescence emission, lifetime, anisotropy, and two-photon absorption (2PA) cross section. They were found to possess high thermal stability, high photostability, high fluorescence quantum yields, and generally large two-photon absorption cross sections, making them quite suitable for new probes in single-photon absorption and two-photon absorption fluorescence microscopy imaging. Novel …

Noncovalent Interaction Of Platinum Planar Amine Compounds With Tryptophan: A Strategy To Interfere With P53-Mdm2 Interactions And Targeting Retroviral Zn Finger-Dna Interaction (Hiv Ncp7), Aaron Bate

Theses and Dissertations

Non-covalent interactions involving π-π stacking play an essential role in self-assembly and molecular recognition processes such as protein folding and DNA/RNA-protein selective recognition. The knowledge gained from these studies could provide insight into possible site recognition complexes, inhibiting or mimicking protein-protein or protein-DNA interactions. Based on molecular modeling as well as HOMO and LUMO energies, several chromophores were selected with a variety of ∆ε values (∆ε= |εHOMO,NAcTrp – εLUMO,chromophores|), high and low, to establish a correlating trend with the modeling and experimental data. The corresponding Pt(dien) compounds were synthesized and their ability to stack to N-acetyl tryptophan was evaluated by …

Highly Stereoselective B-Lactam Synthesis Via The Staudinger Reaction Using Poly Aromatic Imines, Debasish Bandyopadhyay, Monica Xavier, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Highly stereoselective synthesis of a few trans 3-phthalimido substituted B-lactams has been achieved following Staudinger reaction.

Synthetic Studies And Biological Evaluation Of Imidazole-Containing Marine Alkaloids, Lesley Ann Schmid

Chemistry & Biochemistry Dissertations - Archive

This dissertation discusses the synthetic methods towards and the preliminary biological studies of an unnamed, imidazole-containing alkaloid, derived from the marine species Oceanapia. This alkaloid was first discovered in 1996 by researchers at the NIH as a possible inhibitor of the key enzyme in the detoxification cycle of Mycobacterium tuberculosis. Chapter 1 provides an overview of tuberculosis, which is currently the second highest cause of death worldwide, with one third of the world's population infected. In recent years, the emergence of multi-drug resistant strains has created new interest and funding for tuberculosis research. New treatments like the alkaloid described above …

Methods Development In Qualitative And Quantitative Proteomics, Ting Liu

University of Kentucky Doctoral Dissertations

Proteomics based on liquid chromatography coupled to mass spectrometry has developed rapidly in the last decade and become a powerful tool for protein mixtures analysis. LC-MS based proteomics involves four steps, sample preparation, liquid chromatography, mass spectrometry and bioinformatics. Improvements in each step have extended its applications to new biological research areas. This dissertation mainly focuses on method developments in both qualitative and quantitative proteomics.

The first part of this dissertation focuses on qualitative analysis of T. gondii Parasitophorous Vacuole Membrane (PVM) proteins, which is very important for T. gondii’s survival. The hypothesis of this study is that proteomic …