Chemistry Commons^™

Synthesis, Characterization And Potential Applications Of Palladium And Ruthenium Nanostructures, Clara Patrice Adams

Dissertations

Controlling the size and shape of metal nanostructures is important for tuning the intrinsic chemical and physical properties of materials, and consequently their potential technological applications. Modulating the morphology of metal nanostructures is essential to understanding the structure-function relationship (for example, optical, magnetic, catalytic, and electronic properties) under various environmental conditions. Our work describes the development of new procedures for the synthesis of well-defined isotropic and anisotropic nanoparticles consisting of palladium (Pd) and ruthenium (Ru). Characterization of the nanostructures was carried out using transmission electron microscopy (TEM), high resolution-TEM (HRTEM), powder x-ray diffraction (XRD), selected area electron diffraction (SAED) and …

Synthesis And Purification Of A Nucleoside Platinum Complex That Promotes Dna Cross-Linking, Ryan Spear

Honors Theses

Cancer is a deadly and ever present disease in humans and its treatment has become a focus of many types of research. This project was designed to synthesize a platinum complex that will cross-link DNA and in turn cause cell death for rapidly dividing cells (usually cancer cells). The target compound strongly resembled the structure of a nucleic acid, thymidine. Further, nucleic acids are extremely important to cell life and cell membranes have transporters specific for them. Therefore, the purpose to exploring this new platinum complex was to create compound that a cell can easily transport inside its cell and …

Photoreactions Of A Water Soluble Poly-Isoquinolpyrrole With Plasmid Dna, Gregory Versteeg

Honors Theses

With the goal of creating a porphyrin we reacted isoquinol pyrrole, p-fluorobenzaldehyde, and boron trifluoride etherate under appropriate conditions. Instead of a porphyrin being synthesized, we created polyisoquinol pyrrole in high yield and with great absorption properties around 600nm. We characterized this compound via UV/vis spectroscopy, proton NMR, and electrochemistry. The compound was then reacted with [Ru(bipy)2Cl2] to create a cationic compound and this molecule was tested as a possible photosensitizer for photodynamic therapy (PDT) but it was unable to photocleave plasmid DNA above 550nm. The original compound was then methylated and this new compound was also tested as a …

Section Abstracts: Chemistry

Virginia Journal of Science

Abstracts of the Chemistry Section for the 92nd Annual Meeting of the Virginia Academy of Science, May 13-15, 2014, Virginia Commonwealth University, Richmond, Virginia

A Meta Analysis Of Pancreatic Microarray Datasets Yields New Targets As Cancer Genes And Biomarkers, Nalin C. W. Goonesekere, Xiaosheng Wang, Lindsey Ludwig, Chittibabu Guda

Faculty Work

The lack of specific symptoms at early tumor stages, together with a high biological aggressiveness of the tumor contribute to the high mortality rate for pancreatic cancer (PC), which has a five year survival rate of less than 5%. Improved screening for earlier diagnosis, through the detection of diagnostic and prognostic biomarkers provides the best hope of increasing the rate of curatively resectable carcinomas. Though many serum markers have been reported to be elevated in patients with PC, so far, most of these markers have not been implemented into clinical routine due to low sensitivity or specificity. In this study, …

Sdsl-Epr Structural Studies Of The Cytoplasmic Helix In Novel Full-Length Constructs Of The Influenza A M2 Protein, Megan E. Thompson , '14

Senior Theses, Projects, and Awards

The M2 protein of the influenza A virus is a homotetrameric transmembrane proton channel implicated in several stages of the viral replication process. Each of its 97-residue monomers is known to include a transmembrane α-helix. but the structures of the N- and C-terminal domains have not yet been solved. A significant barrier to an atomic level understanding of the M2 protein is the difficulty associated with expression and purification of the full-length protein, which has primarily been studied in the form of truncated constructs covering the amphipathic helix and a short C-terminal segment. This C-terminal segment, which includes residues 46-62, …

Classifying The Functionality Of Primosome Protein A In Deinococcus Radiodurans, Jacob Boone

Honors Theses

Deinococcus radiodurans is an extremophile bacterium with the capacity to withstand tremendous DNA damage that causes disruption of replisome complex activity. The efficiency of origin-independent replisome reloading directly correlates to effectiveness of DNA damage coping strategies, and remains largely undefined in D. rad primosome components. Investigation of D. rad PriA as a helicase protein was conducted to determine if PriA could be classified as a fossilized helicase. This project tested the three functions of known helicases by comparing E. coli and D. rad PriA. DNA binding, DNA unwinding, and ATP hydrolysis assays were performed on both proteins separately and results …

Synthesis And Characterization Of Three Unique Mono-Metallic Lanthanide Complexes, Jasminder S. Grewal

Honors Theses

Three unique lanthanide complexes of formula Ln(tdh)3dpp (where Ln = Eu3+, Tb3+or Nd3+; tdh = 1,1,1- trifluoro-5,5-dimethyl-2,4-hexanedione and dpp = 2,3-Bis(2-pyridyl)pyrazine) were structurally characterized. X-ray quality crystals were grown through slow evaporation in a solution of concentrated ethyl acetate and hexanes. Each of the metals are eight coordinate, with 6 oxygen atoms from the tdh ligand and two nitrogen atoms from the dpp. Specifically, the nitrogen from 1-pyridyl group and the 1-pyrazine group coordinate to the lanthanide metal. Luminescent studies were performed on all three compounds. The Eu and Tb complexes were able to emit light in the visible region …

Design And Characterization Of Photoresponsive Supramolecular Aggregates, Julie A. Fitz

Honors Theses

Supramolecular chemistry concerns the manner in which molecular building blocks associate via non-covalent interactions and form aggregates. The particular building block in this research is a photoresponsive molecule 4,4’-azobenzene dicarboxylic acid (ADA), a molecule that isomerizes reversibly around an N-N double bond upon irradiation with different wavelengths of light. The large structural changes in the molecule that result from isomerization have the potential to modulate the properties of a supramolecular aggregate. ADA was studied under a variety of environmental conditions for the purpose of understanding aggregation behavior and geometries. A UV-Vis and Circular Dichroism (CD) spectroscopic study of ADA showed …

Investigating Bacterial Replication Restart: Can D.Rad Pria Load D.Rad Dnab Onto Dna Forks With A Leading Strand Gap?, Michael Ryan

Honors Theses

The bacteria Deinococcus radiodurans (D. rad) is able to survive multiple double stranded breaks to its DNA with no detriment to its health as its genome can be fully repaired in a matter of hours. During bacterial DNA replication, points of DNA damage can cause replication to cease, requiring an origin independent replisome loading pathway to resume the replication. This pathway is called replication restart , a highly conserved pathway in bacteria. In the E. coli replication restart pathway primosome proteins function by binding to the DNA fork and facilitating the loading of the DnaB helicase onto the replication fork. …

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 …

The Development Of 6.7% Efficient Copper Zinc Indium Selenide Devices From Copper Zinc Indium Sulfide Nanocrystal Inks, Brian Kemp Graeser

Open Access Theses

As solar cell absorber materials, alloys of CuIn(S,Se)2 and Zn(S,Se) provide an opportunity to reduce the usage of indium along with the ability to tune the band gap. Here we report successful synthesis of alloyed (CuInS2 )0.5(ZnS)0.5 nanocrystals by a method that solely uses oleylamine as the liquid medium for synthesis. The reactive sintering of a thin film of these nanocrystals via selenization at 500 °C results in a uniform composition alloy (CuIn(S,Se)2 )0.5 (Zn(S,Se)) 0.5 layer with micron size grains. Due to the large amount of zinc in the film, the sintered grains exhibit the zinc blende structure instead …

Investigation Of Isotope Effects Of Ozone As A Function Of Temperature, Daniel J. Mcmahon

Open Access Theses

Ozone is an important oxidizer in the atmosphere and plays a crucial role as a cleanser, removing various compounds such NOx and SOx. It also is intriguing to those that study stable isotopes as it has a unique signature found in no other oxygen containing molecule. Ozone is observed to fractionate mass independently, which means it does not follow the typical δ 17 O /δ18 O = 0.52 ratio expected for molecules enriched with 17 O and 18 O. The magnitude of ozone's mass independent enrichment has been studied in laboratory experiments and atmospheric observations but its explanation is still …

Applications Of Calculated Second Harmonic Generation Tensors On Monomolecular And Bimolecular Systems, Gregory R. Snyder

Open Access Theses

The field of nonlinear optics (NLO) has proven itself as a relatively recent and powerful area of science in the areas of microscopy and high-sensitivity quantification measurements. In particular, symmetry selective NLO processes such as second harmonic generation (SHG) take advantage of symmetry rules to cancel background noise almost completely, leading to both high resolution images and limits of detection (LOD) in the photon counting range. Background noise in SHG is negated as result of signal cancellation in systems containing inversion symmetry; generally isotropic sources. Quantum mechanical computational chemistry has enriched the field of NLO by enabling studies on hypothetical …

Protein Affinity Extraction Of Prostate Specific Antigen (Psa) Using Submicron Spheres, Yao Wang

Open Access Theses

PSA has been used as a biomarker for prostate cancer for a long time. To characterize different glycoforms of PSA using techniques like UHPLC and cIEF, concentration and purification of PSA from complex samples becomes necessary. Our group has developed submicron silica spheres based affinity beads to extract PSA through immunoprecipitation. This study focuses on measuring the bead performance when antibody type/amount was varied and PSA concentration was lowered for clinical use. To better satisfy the requirement of large-scale extraction, several attempts were made to increase the bead capacity. The results will be presented and future directions of the project …

Reactivity Studies Of Tridhydropyridine Radical Cautions By Using Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry And Advancement Of Mass Spectrometric Analysis Of Asphaltenes And Degradation Products, Mohammad Sabir Aqueel

Open Access Dissertations

Aromatic organic molecules which have unpaired electrons play an important role in a variety of applications in the fields of organic synthesis, organic magnets, and biological activity of organic compounds. Several studies have been published on σ- type carbon-centered mono- and biradicals. Reactive intermediates with three formally unpaired electrons are known as triradicals. They can be defined as species with three electrons distributed in three degenerate or nearly degenerate orbitals, based on Salem's definition of biradicals from the electronic structure point of view. Very little is known about the reactivity of carbon-centered σ,σ,σ- triradicals due to the complexity of studying …

Chemical Literature Databases: Conflict Of Interest?, Belinda L. Hurley

Library Philosophy and Practice (e-journal)

A publisher of a research database controls the search algorithms of its database and, at a minimum, partially controls the indexing metadata attached to journal articles indexed in its database. A publisher of a journal partially controls the indexing metadata attached to articles in that journal. A publisher who publishes both a research database and journals that are indexed in that database has significant control over two major aspects of the discovery process. This allows the possibility for a publisher to introduce a bias into its algorithm that could favor discovery of its own articles. This work looks at search …

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 …

Fundamental Studies Of Protein Ionization For Improved Analysis By Electrospray Ionization Mass Spectrometry And Related Methods, Kevin A. Douglass

Dissertations

Mass spectrometry (MS) is an analytical technique in which a sample is converted to gas-phase ions that are subsequently separated and detected. It offers great speed, selectivity, and sensitivity during analysis, characteristics which have enabled it to become a leading method for the study of proteins. The applications of MS for these biologically significant macromolecules range from accurately determining identity and sequence to shedding light on post-translational modifications and protein-molecule interactions. As a first step towards analysis by MS, gas-phase protein ions must be formed. A common method for ionization is electrospray ionization (ESI), where a liquid sample including the …

Volume 06, Kristen Gains, Amanda Willis, Holly Backer, Monika Gutierrez, Cara O'Neal, Sara Nelson, Sasha Silberman, Jessica Beardsley, Jamie Gardner, Edward Peeples, Matthew Sakach, Tess Lione, Emily Wilkins, Kelsey Holt, Jessica Page, Jamie Clift, Charles Vancampen, Gilbert Hall, Jenny Nehrt, Kasey Dye, Amanda Tharp, Jamie Leeuwrik, Ashley Mcgee, Emily Poulin, Michael Kropf, Nick Pastore, Austin Polasky, Morgan Glasco, Laura L. Kahler, Melinda L. Edwards, Brandon C. Smith, Mariah Asbell, Cabell Edmunds, Amelia D. Perry, Alyssa Hayes, Irina Boothe, Perry Bason, James Early

Incite: The Journal of Undergraduate Scholarship

Introduction from Dean Dr. Charles Ross

Caught Between Folklore and the Cold War: The Americanization of Russian Children's Literature by Kristen Gains

Graphic Design by Amanda Willis

Graphic Design by Holly Backer

Prejudices in Swiss German Accents by Monika Gutierrez

Photography by Cara O'Neal

Photography by Sara Nelson

Edmund Tyrone's Long Journey through Night by Sasha Silberman

Photography by Jessica Beardsley

Photography by Jamie Gardner and Edward Peeples

The Republican Razor: The Guillotine as a Symbol of Equality by Jamie Clift

Graphic Design by Matthew Sakach

Genocide: The Lasting Effects of Gender Stratification in Rwanda By Tess Lione and Emily …

Serial Transfer Can Aid The Evolution Of Autocatalytic Sets, Wim Hordijk, Nilesh Vaidya, Niles Lehman

Chemistry Faculty Publications and Presentations

Background: The concept of an autocatalytic set of molecules has been posited theoretically and demonstrated empirically with catalytic RNA molecules. For this concept to have significance in a realistic origins-of-life scenario, it will be important to demonstrate the evolvability of such sets. Here, we employ a Gillespie algorithm to improve and expand on previous simulations of an empirical system of self-assembling RNA fragments that has the ability to spontaneously form autocatalytic networks. We specifically examine the role of serial transfer as a plausible means to allow time-dependent changes in set composition, and compare the results to equilibrium, or "batch" scenarios. …

Synthesis And Characterization Of A Tetra-Ruthenated Naphthylbiliverdin, Ashley M. Berding

Honors Theses

A new naphtylbiliverdin compound has been synthesized which offers intense absorption with the photodynamic therapy window (600 nm – 850 nm). The compound has been characterized by proton NMR, high resolution electrospray mass spectrometry, elemental analysis, and UV/vis spectroscopy. Coordination of four ruthenium(II) polypyridyl complexes was accomplished by standard procedures. The new tetra-ruthenated naphthylbiliverdin was characterized by elemental analysis. Cyclic voltammetry measurements reveal that all four ruthenium moieties are coordinated to the pyridyl groups of the biliverdin compound. The intense metal to ligand charge transfer (MLCT) bands of the peripheral ruthenium groups overshadow the absorption due to the biliverdin compound; …

Prepubertal Exposure To Arsenic(Iii) Suppresses Circulating Insulin-Like Growth Factor-1 (Igf-1) Delaying Sexual Maturation In Female Rats, Michael P. Reilly, James C. Saca, Alina Hamilton, Rene F. Solano, Jesse R. Rivera, Wendy Innis-Whitehouse, Jason Parsons, Robert K. Dearth

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

Arsenic (As) is a prevalent environmental toxin readily accessible for human consumption and has been identified as an endocrine disruptor. However, it is not known what impact As has on female sexual maturation. Therefore, in the present study, we investigated the effects of prepubertal exposure on mammary gland development and pubertal onset in female rats. Results showed that prepubertal exposure to 10 mg/kg of arsenite (As(III)) delayed vaginal opening (VO) and prepubertal mammary gland maturation. We determined that As accumulates in the liver, disrupts hepatocyte function and suppresses serum levels of the puberty related hormone insulin-like growth factor 1 (IGF-1) …

Controlling Competing Phases Of Magnetic Intermetallics And Bioceramics, Jacob D. Mcalpin

Honors Capstones

No abstract provided.

Characterizing The Interactions Between Influenza A M2 Protein And Cholesterol In Membranes, Matthew R. Elkins , '14

Senior Theses, Projects, and Awards

The influenza A M2 protein is 97-residues in length and homotetramerizes to form a proton channel across the viral membrane early in the influenza life cycle. M2 is also implicated in the formation and budding of new viral particles in a process proposed to require membrane cholesterol. A potential cholesterol recognition amino acid consensus (CRAC) immediately C-terminal to the M2 transmembrane domain is thought to mediate the M2-cholesterol interaction. However, the finer details of this interaction are largely unknown. Using site-directed spin labeling (SDSL) and electron paramagnetic resonance (EPR) spectroscopy, this research aims to gain a more detailed understanding of …

Investigation Of Porphyrins As Potential G-Quadruplex Stabilizing Ligands And Fluorescent Probes, Navin C. Sabharwal , '14

Senior Theses, Projects, and Awards

G-quadruplex (GQ) DNA is a non-canonical DNA structure thought to form throughout the human genome. Because the stabilization of quadruplexes formed in the telomeres and in the promoters of oncogenes may prevent the spread of cancer cells, there is great interest in developing and studying molecules that may bind to and stabilize these unique DNA structures. This thesis investigates the interactions between porphyrins and GQ DNA with the goal of determining how strongly and selectively porphyrins can stabilize the quadruplex structure. There is also great interest in developing luminescent probes for GQ structures to allow for their detection in vivo. …

Probing And Characterizing Different Conformations Of The Influenza A M2 Protein Using Sdsl-Epr Spectroscopy, Sangwoo Shawn Kim , '14

Senior Theses, Projects, and Awards

The M2 protein is a 97-residue membrane homotetrameric protein found on the viral coat of the Influenza A virus. M2 plays a key role in virulence of the Influenza A virus. M2 was previously shown to act as a proton channel that can acidify a virion once it has entered the cell. Recently, M2 has also been implicated in generating curvature in the cell membrane to mediate budding of new viral progeny. Furthermore, the amino acid sequence of M2 contains a cholesterol recognition amino acid consensus (CRAC) domain, which indicates that M2 may interact with cholesterol. In this thesis, site-directed …

Spectroscopy Duplication I, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

Synthesis And Evaluation Of 3-Aryl-4(1h)-Quinolones As Orally Active Antimalarials: Overcoming Challenges In Solubility, Metabolism, And Bioavailability, Andrii Monastyrskyi

USF Tampa Graduate Theses and Dissertations

Infectious diseases are the second leading cause of deaths in the world with malaria being responsible for approximately the same amount of deaths as cancer in 2012. Despite the success in malaria prevention and control measures decreasing the disease mortality rate by 45% since 2000, the development of single-dose therapeutics with radical cure potential is required to completely eradicate this deadly disease. Targeting multiple stages of the malaria parasite is becoming a primary requirement for new candidates in antimalarial drug discovery and development. Recently, 4(1H)-pyridone, 4(1H)-quinolone, 1,2,3,4-tetrahydroacridone, and phenoxyethoxy-4(1H)-quinolone chemotypes have been shown to be antimalarials with blood stage activity, …

Insights Into [Aacute]-Aa Peptides And Ã-Aa Peptides As Broad Spectrum Antimicrobial Peptidomimetics And As Anti-Biofilm Agents, Shruti Padhee

USF Tampa Graduate Theses and Dissertations

The emergent resistance of bacteria against the conventional antibiotics has motivated the search for novel antimicrobial agents. Nature abounds with a number of antimicrobial peptides that are a part of our innate immune system and protect us against a variety of pathogenic bacteria. While they are broad-spectrum in their activity and show less drug-resistance induction, their intrinsic metabolic stability limits their potential therapeutic applications. Herein we describe the development of novel broad-spectrum bioactive antimicrobial peptidomimetics AA-peptides. AApeptides were designed based on chiral PNA backbone. Substitution of nucleobases yields AApeptides that are resistant to proteolysis and capable of mimicking peptides. Two …