Digital Commons Network^™

Strategies For Labeling Proteins With Paracest Agents, Olga Vasalatiy, Piyu Zhao, Mark Woods, Andrei Marconescu, Aminta Castillo-Muzquiz, Philip Thorpe, Garry Kiefer, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Reactive surface lysine groups on the chimeric monoclonal antibody (3G4) and on human serum albumin (HSA) were labeled with two different PARACEST chelates. Between 7.4 – 10.1 chelates were added per 3G4 molecule and between 5.6 – 5.9 chelates per molecule of HSA, depending upon which conjugation chemistry was used. The immunoreactivity of 3G4 as measured by ELISA assays was highly dependent upon the number of attached chelates: 88% immunoreactivity with 7.4 chelates per antibody versus only 17% immunoreactivity with 10.1 chelates per antibody. Upon conjugation to 3G4, the bound water lifetime of Eu-1 increased only marginally, up from …

Inducible Nitric Oxide Synthase Provides Protection Against Injury-Induced Thrombosis In Female Mice, Rita K. Upmacis, Hao Shen, Lea Esther S. Benguigui, Brian D. Lamon, Ruba S. Deeb, Katherine A. Hajjar, David P. Hajjar

Faculty Papers and Publications

Nitric oxide (NO) is an important vasoactive molecule produced by three NO synthase (NOS) enzymes: neuronal (nNOS), inducible (iNOS) and endothelial NOS (eNOS). While eNOS contributes to blood vessel dilation that is generally thought to protect against the development of hypertension, iNOS has been primarily implicated as a disease-promoting isoform leading to protein-bound 3-nitrotyrosine formation in aortic lesions and select organs during atherogenesis. Despite this, iNOS may also play a physiological role, via the modulation of cyclooxygenase and thromboregulatory eicosanoid production. Herein, we examined the role of iNOS in a murine model of thrombosis. Blood flow was measured in carotid …

Synthesis Of Alkynyl Ribofuranosides, Christian Rodriguez

Dissertations and Theses

No abstract provided.

Methionine-35 Of Aβ(1-42): Importance For Oxidative Stress In Alzheimer Disease, D. Allan Butterfield, Rukhsana Sultana

Chemistry Faculty Publications

Alzheimer disease (AD) is an age-related progressive neurodegenerative disorder. This devastating disease is characterized by the presence of senile plaques (SP), neurofibrillary tangles (NFTs), and loss of synapses. Amyloid beta-peptide 1–42 (Aβ(1–42)) is the main component of SP and is pivotal to AD pathogenesis. Brain of subjects with AD and arguably its earliest manifestation, mild cognitive impairment (MCI), demonstrate increased levels of oxidative stress markers. Our laboratory combined these two aspects of AD and MCI and proposed the Aβ(1–42)-associated free radical oxidative stress hypothesis to explain oxidative stress under which the MCI and AD brain exist …

The Release Of Calcium In Bacillus Anthracis Pathogenicity, Natiera Magnuson, Manomita Patra, Maria Elena Reynaga, Ernesto Abel-Santos

McNair Poster Presentations

Bacillus anthracis spores form in response to starvation and can withstand extremes of heat, radiation, and chemical toxins, making B. anthracis spores ideal vehicles for infections.1 The resistance and dormancy of bacterial spores are dependent on a largely dehydrated core.2 The spore core is not only devoid of water, but contains between 0.8 to 1M calcium complexed with 2,6-pyridinedicarboxylic acid (dipicolinic acid, DPA). The DPA-calcium complex (CaDPA) helps protect DNA, RNA, and the metabolic enzymes needed for the establishment of a vegetative cell cytoplasm.3 An anthrax infection starts with the germination of B. anthracis spores in a macrophage.4 The germinated …

Synthesis, Assembly, And Characterization Of Monolayer-Protected Gold Nanoparticle Films For Protein Monolayer Electrochemistry,, Tran T. Doan, Michael H. Freeman, Adrienne R. Schmidt, Natalie T. Nguyen, Michael C. Leopold

Chemistry Faculty Publications

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified …

Charge Saturation And Neutral Substitutions In Halomethanes And Their Group 14 Analogues, Bernard K. Wittmaack, Chad Crigger, Matthew Guarino, Kelling J. Donald

Chemistry Faculty Publications

A computational analysis of the charge distribution in halomethanes and their heavy analogues (MH_4-nX_n: M= C, Si, Ge, Sn, Pb; X = F, Cl, Br, I) as a function of _n uncovers a previously unidentified saturation limit for fluorides when M ≠ C. We examine the electron densities obtained at the CCSD, MP2(full), B3PW91, and HF levels of theory for 80 molecules for four different basis sets. A previously observed substituent independent charge at F in fluoromethanes is shown to be a move toward saturation that is restricted by the low polarizability of C. This limitation …

Method Developments To Analyze Caffeine And Acesulfame-K Concentrations In Natural Waters In And Around Charleston, Il, Usa, Laleen Bodhipaksha

Masters Theses

Analytical methods using batch solid phase extraction were developed for two chemical markers, caffeine and acesulfame-K, to assess anthropogenic water contamination of natural water bodies in and around Charleston, Illinois.

Measurements were conducted on 12 different extracted samples using reverse phase HPLC. Two creek samples showed the presence of acesulfame-K (0.45 ± 0.10 and 0.25 ± 0.06 ppb) and two creek samples showed the presence of caffeine (3 .1 ± 1.2 and 1.6 ± 0.6 ppb ). Effluent from the Charleston waste water treatment plant showed an acesulfame-K concentration of 0.67 ± 0.15 ppb.

These results indicate measurement of both …

Synthesis Of Molecular Containers Based On Modifications Of Resorcin(4)Arene And Calix(4)Arene, Anupama Makineni

Masters Theses

This research work was mainly focused on the synthesis of molecular containers based on modifications ofresorcin[4]arene and calix[4]arene.

The modifications of resorcin[ 4 ]arene include the attempts to attach a phthalimide featured linker onto the phenol hydroxyl groups of resorcin[4]arene. A few halogen leaving groups were used, including fluorine, chlorine, and bromine. The substitution with tetraflorophthalimide resulted in a mixture of regio-isomeric products, whereas for 4,5-dichloro- and 4,5-dibromophthalimides, no desired substitution product was formed. It was, however, discovered that both 4,5-dichloro- and 4,5-dibromophthalimides forms monoclinic crystals. The second modification of resorcin[4]arene focused on functionalizations of both upper and lower rims …

Self-Assembly And Photophysics Of Selected Organic Materials And Two-Photon Bioimaging With Profluorescent Nitroxides, Polyelectrolyte Nanoparticles, And Squaraine Probes, Hyo Yang Ahn

Electronic Theses and Dissertations

Two-photon absorption and upconverted fluorescence has been utilized in a variety of applications in pure science and engineering. Multiphoton-based techniques were used in this research in order to understand photophysical and chemical characteristics of several fluorescent dyes and to demonstrate some of their key applications. Two-photon fluorescence microscopy (2PFM) has become a powerful technique in bio-photonics for non-invasive imaging in the near-infrared (NIR) region (700~1000 nm) that often results in less photobleaching. In Chapter 1, there is a brief introduction to fluorescence, examples of fluorescence materials, and a discussion of the advantages of two-photon absorption. 2PFM imaging was utilized in …

The Application Of Two-Photon Absorbing Probes In Lysosomal, Zinc Ion Sensing And Folate Receptor-Targeted Bioimaging, Xuhua Wang

Electronic Theses and Dissertations

Two-photon fluorescence microscopy (2PFM) has become a powerful technique for bioimaging in non-invasive cancer diagnosis and also investigating the mechanization and original of a variety of diseases by tracking various biological processes. Because the fluorescence emission by two photon absorbing (2PA) is directly proportional to the square of the intensity of excitation light, this intrinsic property of 2PA provides 2PFM great advantages over traditional one-photon fluorescence microscopy (1PFM), including high 3D spatial localization, less photodamage and interference from biological tissue because of using longer wavelength excitation (700-1300 nm). However, most 2PA probes are hydrophobic and their photostabilities are questionable, severely …

The Unsuspected Pathway Of The Allosteric Transition In Hemoglobin, Stefan Fischer, Kenneth W. Olsen, Kwangho Nam, Martin Karplus

Chemistry: Faculty Publications and Other Works

Large conformational transitions play an essential role in the function of many proteins, but experiments do not provide the atomic details of the path followed in going from one end structure to the other. For the hemoglobin tetramer, the transition path between the unliganded (T) and tetraoxygenated (R) structures is not known, which limits our understanding of the cooperative mechanism in this classic allosteric system, where both tertiary and quaternary changes are involved. The conjugate peak refinement algorithm is used to compute an unbiased minimum energy path at atomic detail between the two end states. Although the results confirm some …

Detecting Specific Saccharides Via A Single Indicator, Soojin Lim, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin

Chemistry Faculty Publications and Presentations

An improved synthesis of a rhodamine boronic acid indicator is reported. This compound is used in an optimized data collection protocol for wavelength- and time-dependent selectivity of sugars such as fructose and ribose derivatives. One indicator is thus used to selectively distinguish structurally related sugar analytes.

The Relative Recoverability Of Dna And Rna Profiles From Forensically Relevant Body Fluid Stains, Charly Parker

Electronic Theses and Dissertations

Biological material (fluids or tissues) whether from the victim or suspect is often collected as forensic evidence, and methods to obtain and analyze the DNA found in that material have been well established. The type of body fluid (i.e. blood, saliva, semen, vaginal secretions, and menstrual blood) from which the DNA originated is also of interest, and messenger RNA typing provides a specific and sensitive means of body fluid identification. In order for mRNA profiling to be utilized in routine forensic casework, RNA of sufficient quantity and quality must be obtained from biological fluid stains and the methods used for …

The Study Of Three Different Layered Structures As Model Systems For Hydrogen Storage Materials, Muzaffer Tonguç Öztek

Electronic Theses and Dissertations

The strength and success of the hydrogen economy relies heavily on the storage of hydrogen. Storage systems in which hydrogen is sequestered in a solid material have been shown to be advantageous over storage of hydrogen as a liquid or compressed gas. Many different types of materials have been investigated, yet the desired capacity and uptake/release characteristics required for implementation have not been reached. In this work, porphyrin aggregates were investigated as a new type of material for hydrogen storage. The building blocks of the aggregates are porphyrin molecules that are planar and can assume a face to face arrangement …

Synthesis Of Chiral Ferrosalen Ligands And Their Applications In Asymmetric Catalysis, Xiang Zhang

Dissertations, Master's Theses and Master's Reports - Open

A new series of chiral ferrosalen ligands was designed and synthesized. The special feature of the ferrosalen ligands is that the chirality originated from the planar chiral ferrocenyl structure. For most known salen ligands, chirality comes from central and axial chiral centers. The key building block for the construction of these ferrosalen ligands was synthesized stereoselectively by a chiral auxiliary approach. This approach does not consume any chiral material, and does not require chiral HPLC resolution. Using this method, nine ligands were prepared using ferrocene as the starting material. In addition, the steric hindrance was modulated by changing the cyclopentadienyl …

Recent Advances In The Synthetic And Mechanistic Aspects Of The Ruthenium-Catalyzed Carbon-Heteroatom Bond Forming Reactions Of Alkenes And Alkynes, Chae S. Yi

Chemistry Faculty Research and Publications

The group’s recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C–O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy₃)₂(CO)RuHCl was found to be a highly effective catalyst for the regioselective alkyne-to-carboxylic acid coupling reaction in yielding synthetically useful enol ester products. Cationic ruthenium-hydride catalyst generated in-situ from (PCy₃)₂(CO)RuHCl/HBF₄·OEt₂ was successfully utilized for both the hydroamination and related C–N bond forming reactions of alkenes. For …

Cell And Protein-Based Sensing Systems For The Detection Of Environmentally And Physiologically Relevant Molecules, Kendrick Bruce Turner

Theses and Dissertations--Chemistry

The detection of small molecules in complex sample matrices such as environmental (surface and ground water, sediment, etc.) and biological (blood, serum, plasma, etc.) samples is of paramount importance for monitoring the distribution of environmental pollutants and their patterns of exposure within the population as well as diagnosing and managing diseases. Biosensors have demonstrated a singular ability to sensitively and selectively detect analytes in complex samples without the need for extensive sample preparation and pretreatment. Nature has demonstrated myriad examples of exquisite selectivity in spite of complexity and we seek to take advantage of that attribute in the development of …

Semiconducting Polymers And Block Copolymers Prepared By Chain-Growth Living Polymerization, Jinwoo Choi

LSU Doctoral Dissertations

Organic semiconducting polymers are the unique materials that considered a basis for the next generation of electronic and optoelectronic applications. However, high device performance of semiconducting polymers strongly depends on their molecular structure and nanoscale organization. Therefore, it is an essential task to develop robust and versatile synthetic approaches to build such well-defined semiconducting polymer materials. This Ph.D. study aimed at design of state-of-the-art synthetic approaches towards organic semiconducting polymers via chain-growth living polymerization as well as development of polymer architectures which can self-organize into supramolecular nanoassemblies or allow external control of the polymer’s properties. First, we prepared a series …

Application Of Scanning Probe Microscopy For New Physical Measurements And Studies Of Surface Chemical Reactions Of Materials At The Molecular Level, Stephanie Loletha Daniels

LSU Doctoral Dissertations

Scanning probe microscopy (SPM) provides unique capabilities for surface visualization and measurements that reach atomic and molecular dimensions. My research focus is directed toward applying and developing new measurements for analytical and surface chemistry with SPM. Two distinct goals based on studies with atomic force microscopy (AFM) will be described within this dissertation. The primary goal was to develop and apply a new AFM imaging mode for ultrasensitive measurements of the superparamagnetic properties of proteins. Magnetic sample modulation (MSM)-AFM, has capabilities to investigate and map the magnetic response of nanomaterials with unprecedented spatial resolution. The second goal was to apply …

Design And Construction Of A Reflectron Time Of Flight Mass Spectrometer For Multiphoton Ionization And Vibrational Spectroscopic Studies Of Mass-Selected Clusters, Matthew Dodd Mcdowell

Honors Theses

Mass spectrometry is typically employed for the elucidation and identification of elements and compounds. Its ability to select and isolate specific molecular clusters makes it an ideal tool for the fundamental spectroscopic study of the photophysical and geometric properties of molecules and molecular clusters. The design and construction of a reflectron time of flight mass spectrometer (reflectron TOF-MS) as well as its implementation for electronic and vibrational spectroscopic studies of various molecules and molecular clusters is discussed. The first chapter introduces basic theory related to electronic spectroscopy, multiphoton ionization, and vibrational spectroscopy. The second chapter entails the theoretical aspects of …

Alteration Of Hydrogen Bonding In The Vicinity Of Histidine 48 Disrupts Millisecond Motions In Rnase A, Nicolet Doucet, Gennady Khirich, Evgenii L. Kovrigin, J. Patrick Loria

Chemistry Faculty Research and Publications

The motion of amino acid residues on the millisecond (ms) time scale is involved in the tight regulation of catalytic function in numerous enzyme systems. Using a combination of mutational, enzymological, and relaxation-compensated ¹⁵N Carr−Purcell−Meiboom−Gill (CPMG) methods, we have previously established the conformational significance of the distant His48 residue and the neighboring loop 1 in RNase A function. These studies suggested that RNase A relies on an intricate network of hydrogen bonding interactions involved in propagating functionally relevant, long-range ms motions to the catalytic site of the enzyme. To further investigate the dynamic importance of this H-bonding network, this …

Development Of A Versatile Man-Portable Obscurant Aerosol Generator: Characterization Of Aerosols In Laboratory And Field Environments, Robert William Schaub

Doctoral Dissertations

"The objective of research presented in this dissertation was to develop a readily deployable and environmentally benign obscurant system operating with a single liquid for the visible and near infrared regions. To achieve this objective, research efforts were directed in two areas: i. Evaluating suitable biogenic oils to replace the United States Army's "Fog Oil" as the obscurant fluid. ii. Design, fabrication and validation of a prototype man-portable / vehicle mountable modular obscurant aerosol generator. Petroleum middle distillate - "Fog Oil" has been the material of choice for wide area obscuration for several decades. Large quantities (thousands gallons) of the …

Preliminary Model Development Of Metal Complexation Of Polyester Derivatives Of 2,2'-Biimidazole, Shelonda Rena Taylor Finch

Doctoral Dissertations

"The objective of this study was to develop a chemical model for metal ion complex formation by a macroligand system with multi-metal binding sites using 2,2'-biimidazole as the starting molecule of the ligand system. Prior studies in this laboratory guided the selection of diesters and hydroxyethyl derivatives of 2,2'-biimidazole as model monomers. In addition, metal ion complexation studies with 2,2'-biimidazole derivatives were conducted. As a result, crystal structures of 1,1'-di(methylpropionato)-2,2-biimidazole, 2,2'-bis(1H-imidazolium) dinitrate and silver 2,2'-bis(1H-imidazolium) trinitrate, were reported. The crystal structures indicated a dependence upon the binding ability of the protonated 2,2'-biimidazole and counter ions. transesterification of the diesters and …

An Easy And Straightforward Route For The Synthesis Of Disubstituted Imidazoles, Debasish Bandyopadhyay, Yvette Mora, Jesus A. Trevino-Cantu, Bimal K. Banik

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

A simple and high-yielding procedure has been developed to synthesize disubstituted imidalozes using phenyl glyoxal monohydrate, ammonium acetate and aldehydes. This synthetic protocol allows the preparation of a variety of 2,4 (s)-disubstituted imidalozes without using any catalyst, expensive or sensitive reagents. A corresponding 2-aroyl-4(s) disubstituted imidalozes derivative has also been isolated as byproduct. The effects of solvents have also been studied.

Microwave-Induced N-Bromosuccinimide-Mediated Novel Synthesis Of Pyrroles Via Paal-Knorr Reaction, Rosemarie Andoh-Baidoo, Roberto Danso, Sanghamitra Mukherjee, Debasish Bandyopadhyay, Bimal K. Banik

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

An expeditious rapid synthesis of N-substituted pyrroles using microwave-induced Nbromosuccinimide- mediated solventless reaction of 2,5-hexanedione and primary amine has been accomplished.

Microwave-Induced Indium-Catalyzed Synthesis Of Pyrrole Fused With Indoline In Water, Dina Abrego, Debasish Bandyopadhyay, Bimal K. Banik

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

An expeditious microwave-induced indium metal-catalyzed synthesis of pyrrole fused with indoline in water is developed by reacting isatin and 4-hydroxyproline.

Microwave-Induced Bismuth Nitrate-Catalyzed Expeditious Enamination Of Β-Dicarbonyl Compounds Under Solvent-Free Conditions, Debasish Bandyopadhyay, Bimal K. Banik

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

Bismuth nitrate-catalyzed, automated microwave-assisted expeditious synthesis of β- enaminones and β-enaminoesters has been carried out in an efficient manner under solvent-free condition. The reaction is general for primary, secondary (cyclic, heterocyclic and acyclic), benzylic as well as aromatic amines.

Probing Molecules In Confined Space, Carissa Marie Vetromile

USF Tampa Graduate Theses and Dissertations

Despite the plethora of information regarding cellular crowding and its importance on modulating protein function the effects of confinement on biological molecules are often overlooked when investigating their physiological function. Recently however, the encapsulation of biomolecules in solid state matrices (NafionTM, sol-gels, zirconium phosphate,etc.) has increased in importance as a method for examining protein conformation and dynamics in confined space as well as novel applications in biotechnology. Biotechnological applications include, but are not limited to, bioremediation, biosensors, biocatalysts, etc. In order to better utilize solid state materials as substrates for biological molecules an understanding of the effects of encapsulation on …

Evaluation Of The Physicochemical Properties And Stability Of Solid Lipid Nanoparticles Designed For The Delivery Of Dexamethasone To Tumors, Melissa Howard

University of Kentucky Doctoral Dissertations

Pre-clinical and clinical trials suggest that pre-treatment with dexamethasone (Dex) may facilitate enhanced uptake of subsequently administered chemotherapeutic agents. To reduce the side effects associated with systemic administration of Dex, solid lipid nanoparticles (SLNs) containing dexamethasone palmitate (Dex-P) were prepared as a means of achieving tumor-targeted drug delivery. These studies were aimed at evaluating the physicochemical properties and both the physiological and storage stability of the SLNs.

SLNs were prepared using nanotemplate engineering technology. Stearyl alcohol (SA) was used as the lipid phase with Brij^® 78 and Polysorbate 60 as surfactants and PEG6000 monostearate as a long-chain PEGylating agent. …