Chemistry Commons^™

Polyaminocarboxylic Acids As Potential Candidates For Trivalent Actinide/Lanthanide Separations, Daniel Stephen Kissel

Dissertations

Nuclear energy, which has historically been considered an alternative energy solution in the United States, is regaining support as an efficient means of energy production. The viability of nuclear energy for the future, however, will remain suspect until issues involving the waste created are fully addressed in the next generation of advanced nuclear fuel cycles. The TALSPEAK process, developed at Oak Ridge National Laboratory, is a classic solvent extraction technique that employs a series of analytical separations in an effort to remove radioactive contaminants from spent nuclear fuel (SNF) and recover uranium in high purity. This separation utilizes a polyaminocarboxylic …

Microfluidic And Nanofluidic Devices - Mixed Scale Systems For Bioanalytical Applications, Michael David Vincent

LSU Doctoral Dissertations

Developments in the field of microfluidics and nanofluidics allow an experimenter to employ new analytical techniques. One direction in which the field is moving towards is developing new devices and or instruments on the smallest scale possible. One way in which this can be achieved is by using a combination of top-down and bottom-up technologies. Some of these top-down techniques have been used in other fields such as the use of photolithography to fabricate semiconductors. Photolithography is a top-down method used to create features normally on the micrometer scale, but in order to create nanometer size features another top-down method …

Synthesis, Characterization, And Investigation Of The Catalytic Activity Of Nio, Cuo, And Nio-Cuo Nanoparticles On Silica As Surrogates Of Combustion-Generated Nanoparticles, Nuwan Nilanka Balapitiya Liyanage

LSU Doctoral Dissertations

Transition metal oxide nanoparticles contained in fly ash are known to catalyze the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) during the waste incineration process. The potential catalytic activity of silica-supported NiO, CuO, and NiO-CuO nanoparticles for the formation of PCDD/Fs will be discussed in this dissertation. The successful synthesis of silica-supported NiO, CuO, and NiO-CuO nanoparticles as surrogates of combustion-generated nanoparticles was important to this study. The synthesis was followed by the characterization of the nanoparticle surrogates by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). Finally, the catalytic …

Using Spe And Hplc-Ms To Quantify And Identify Pharmaceutical Compounds In St. John's University Wastewater, Melissa E. Stuckey

Honors Theses, 1963-2015

Pharmaceuticals in wastewater have become a concern of environmental toxicologists. An efficient method of discovering the concentrations of these pharmaceuticals in wastewater has not yet been produced. The method we developed includes an automated Solid Phase Extraction (SPE) procedure prior to injecting a sample of wastewater into the High Performance Liquid Chromatograph (HPLC) and Mass Spectrometer – Electrospray Ionization (MS-ESI). Three unknown peaks were identified on the HPLC and MS from wastewater obtained from the St. John’s Wastewater Treatment Plant in June 2013. Methods of analysis including NMR, GC-MS and IR have been used to determine the composition of these …

Mixed Quantum/Classical Calculations Of Total And Differential Elastic And Rotationally Inelastic Scattering Cross Sections For Light And Heavy Reduced Masses In A Broad Range Of Collision Energies, Alexander Semenov, Dmitri Babikov

Chemistry Faculty Research and Publications

The mixed quantum/classical theory (MQCT) for rotationally inelastic scattering developed recently [A. Semenov and D. Babikov, J. Chem. Phys.139, 174108 (2013)] is benchmarked against the full quantum calculations for two molecular systems: He + H2 and Na + N2. This allows testing new method in the cases of light and reasonably heavy reduced masses, for small and large rotational quanta, in a broad range of collision energies and rotational excitations. The resultant collision cross sections vary through ten-orders of magnitude range of values. Both inelastic and elastic channels are considered, as well as differential (over scattering angle) cross sections. In …

Tandem Mass Spectrometry Of Multiply Charged Polymers: Using Ms3 Strategies For Full Structural Characterization Of Polyacrylamides, Paul M. Krauss

Williams Honors College, Honors Research Projects

In mass spectrometry, a compound is taken and converted into a gas-phase ion by an electrical charge (Balogh, 2009). From these ions, a chart is then created that displays the mass to charge ratio, which is able to then be analyzed to find out the charge of the ions, as well as the mass of the compound (Balogh, 2009). One specific type of mass spectrometry there is available is known as a fragmentation spectrometry. In fragmentation spectrometry, the molecule is not only ionized and analyzed, but fragmented parts that are formed into ions are also ionized and analyzed. This is …

Controlled Release Kinetics In Hydroxy Double Salts: Effect Of Host Anion Structure, Stephen Majoni, Jeanne M. Hossenlopp

Chemistry Faculty Research and Publications

Nanodimensional layered metal hydroxides such as layered double hydroxides (LDHs) and hydroxy double salts (HDSs) can undergo anion exchange reactions releasing intercalated anions. Because of this, these metal hydroxides have found applications in controlled release delivery of bioactive species such as drugs and pesticides. In this work, isomers of hydroxycinnamate were used as model compounds to systematically explore the effects of anion structure on the rate and extent of anion release in HDSs. Following intercalation and subsequent release of the isomers, it has been demonstrated that the nature and position of substituent groups on intercalated anions have profound effects on …

Probing The Human Estrogen Receptor-Α Binding Requirements For Phenolic Mono- And Di-Hydroxyl Compounds: A Combined Synthesis, Binding And Docking Study, Christopher Mccullough, Terrence S. Neumann, Jayapal Reddy Gone, Zhengjie He, Christian Herrild, Julie Lukesh, Rajesh K. Pandey, William A. Donaldson, Daniel S. Sem

Chemistry Faculty Research and Publications

Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. Di-hydroxyl compounds were predicted to bind with their aliphatic hydroxyl group interacting with His524 in ERα. One nonsteroid-based dihdroxyl compound was 1000-fold specific for ERβ over ERα, and …

Assembly, Structure, And Reactivity Of Cu4S And Cu3S Models For The Nitrous Oxide Reductase Active Site, CuZ*, Brittany J. Johnson, Sergey V. Lindeman, Neal P. Mankad

Chemistry Faculty Research and Publications

Bridging diphosphine ligands were used to facilitate the assembly of copper clusters with single sulfur atom bridges that model the structure of the Cu_Z* active site of nitrous oxide reductase. Using bis(diphenylphosphino)amine (dppa), a [Cu^I₄(μ₄-S)] cluster with N–H hydrogen bond donors in the secondary coordination sphere was assembled. Solvent and anion guests were found docking to the N–H sites in the solid state and in the solution phase, highlighting a kinetically viable pathway for substrate introduction to the inorganic core. Using bis(dicyclohexylphosphino)methane (dcpm), a [Cu^I₃(μ₃-S)] cluster was assembled …

Visible-Light Photocatalyzed Cross-Linking Of Diacetylene Ligands By Quantum Dots To Improve Their Aqueous Colloidal Stability, Marion G. Götz, Hiroko Takeuchi, Matthew J. Goldfogel, Julia M. Warren, Brandon D. Fennel, Colin D. Heyes

Chemistry & Biochemistry Faculty Publications and Presentations

Ligand cross-linking is known to improve the colloidal stability of nanoparticles, particularly in aqueous solutions. However, most cross-linking is performed chemically, in which it is difficult to limit interparticle cross-linking, unless performed at low concentrations. Photochemical cross-linking is a promising approach but usually requires ultraviolet (UV) light to initiate. Using such high-energy photons can be harmful to systems in which the ligand–nanoparticle bond is fairly weak, as is the case for the commonly used semiconductor quantum dots (QDs). Here, we introduce a novel approach to cross-link thiolated ligands on QDs by utilizing the photocatalytic activity of QDs upon absorbing visible …

Accurate Calculations Of Rotationally Inelastic Scattering Cross Sections Using Mixed Quantum/Classical Theory, Alexander Semenov, Dmitri Babikov

Chemistry Faculty Research and Publications

For computational treatment of rotationally inelastic scattering of molecules, we propose to use the mixed quantum/classical theory, MQCT. The old idea of treating translational motion classically, while quantum mechanics is used for rotational degrees of freedom, is developed to the new level and is applied to Na + N₂ collisions in a broad range of energies. Comparison with full-quantum calculations shows that MQCT accurately reproduces all, even minor, features of energy dependence of cross sections, except scattering resonances at very low energies. The remarkable success of MQCT opens up wide opportunities for computational predictions of inelastic scattering cross sections …

Investigations Into The Fluorescent Covalent Labeling Of Biomolecules Utilizing Rhodamine Dyes, Electrophilic Leaving Groups And Mrna Display., Susan D. Selaya

Theses and Dissertations

The discovery of a method by which proteins of interest can selectively be labeled with a probe of choice intracellularly is a longstanding goal in chemical biology research. Conventional labeling techniques have utilized large domain tags but despite the development of small labeling molecules there have been no short peptide sequences known to covalently label a small molecule without the aid of an enzymatic process or metal chelation. We aimed to find a sequence of nucleophilic peptides that reacted covalently and specifically with electrophilic small labeling molecules using mRNA display. Our goal was to show that an electrophilic small labeling …

Platinum Complexes And Zinc Finger Proteins: From Target Recognition To Fixation, Samantha Tsotsoros

Theses and Dissertations

Bioinorganic chemistry strives to understand the roles of metals in biological systems, whether in the form of naturally occurring or addition of non-essential metals to natural systems. Metal ions play vital roles in many cellular functions such as gene expression/regulation and DNA transcription and repair. The study of metal-protein-DNA/RNA interactions has been relatively unexplored. It is important to understand the role of metalloprotein interactions with DNA/RNA as this enhanced knowledge may lead to better understanding of diseases and therefore more effective treatments. A major milestone in the development of this field was the discovery of the cytotoxic properties of cisplatin …

The Effects Of Coal Mining On Health In Appalachia : Global Context And Social Justice Implications, Adrienne Schmidt

Honors Theses

The purpose of this report is to investigate the environmental and health effects of coal mining in the Appalachian region of the United States in the context of global natural resource extraction, explore existing regulation for the reduction of negative environmental health effects of mining in Appalachia, and explore the social justice implications of current mining practices. The research for this report was limited to literature published in English. It was found that there are widespread negative health effects of mining in Appalachia due to environmental toxins, a toxic social environment of limited economic opportunity, and occupational health hazards. The …

Electrodeposition And Characterisation Of Copolymers Based On Pyrrole And 3,4-Ethylenedioxythiophene In Bmim Bf4 Using A Microcell Configuration, Lavinia Astratine, Edmond Magner, John Cassidy, Tony Betts

Articles

Electrochemical copolymerization of pyrrole (Py) and 3,4-ethylenedioxythiophene (EDOT) was performed in an ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, (BMIM BF4) employing a ‘micro-cell’ in order to use the materials efficiently. Characterization of the copolymers formed on an ITO substrate was performed for different Py: EDOT ratios (1:2, 1:1, 2:1) in both aqueous and ionic liquid electrolytes. Electrochemical and spectroelectrochemical analysis revealed that the properties of the copolymer depend upon the Py/EDOT monomer ratio used. The copolymer PPy-co-PEDOT (2:1) displayed good stability, a switching time of 20 s and a colouration efficiency of 101.3 C-1cm2. The presence of Py in the copolymer stabilised …

Progress In Zeolite Synthesis Promotes Advanced Applications, Moussa Zaarour, Biao Dong, Izabela Naydenova, Richard Retoux, Svetlana Mintova

Articles

This article outlines the importance of zeolite synthesis and their unique physicochemical characteristics promoting advanced applications. The main strategies for preparation of zeolites including organic-template assisted, organic-template free and alternative procedures are considered for synthesis of crystallites offering control and fine-tuning of their properties. Besides, rational design of zeolites with pre-determined structure, porosity, size, morphology, and composition are more viable by studying carefully the chemical and physical parameters controlling the zeolite synthesis and understanding the crystallization mechanism. Finally, a particular attention to the preparation of zeolites with nanosized dimensions and their utilization in innovative applications including photovoltaic, medicine and holographic …

A Review Of The Hyporheic Zone, Stream Restoration, And Means To Enhance Denitrification, Leanne Merill, David J. Tonjes

Technology & Society Faculty Publications

The hyporheic zone is the subsurface area below and adjacent to a stream where groundwater mixes with stream water, through vertical, lateral, and longitudinal flows. The hyporheic zone connects the stream to uplands and other terrestrial environments. It is a zone of distinct faunal communities, high biological diversity and ecological complexity, and is the site of chemical processing and transformations of ground- and stream waters. The hyporheic zone is important to the overall ecosystem ecology of the stream, and it can influence stream water chemistry. Flows, reactions, and biota in the hyporheic zone are heterogeneous and patchy, making it difficult …

Economic Synthesis Of Quinaldinium Fluorochromate(Vi), (Qnfc), And Solvent-Free Periodic Acid Oxidation Of Alcohols Catalyzed By Qnfc, Melek Özdemi̇r, Hati̇ce Beyti̇ye Özgün

Turkish Journal of Chemistry

A 1:1:1 stoichiometric reaction between CrO_3, aqueous HF, and quinaldine affords orange crystalline quinaldinium fluorochromate(VI) (QnFC) (C_{10}H_9NH[CrO_3F]) in 99.4% isolated yield. A highly efficient, simple, chemoselective, and environmentally benign procedure for QnFC (3 mol%) catalyzed oxidation of primary and secondary alcohols to aldehydes and ketones using 1.1 equiv of H_5IO_6 under solvent-free conditions is described.

Electrochemistry Of Fe(Iv) And Mn(Iv) Corroles Containing Meso-Dichlorophenyl Substituents And The Use Of These Compounds As Catalysts For The Electroreduction Of Dioxygen In Acid Media, Lina Ye, Zhongping Ou, Deying Meng, Mingzhu Yuan, Yuanyuan Fang, Karl M. Kadish

Turkish Journal of Chemistry

Two meso-dichlorophenyl substituted metallocorroles were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in dichloromethane, benzonitrile, and pyridine containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) as supporting electrolyte. The examined compounds are represented as (Cl_2Ph)_3CorFe^{IV}Cl and (Cl_2Ph)_3CorMn^{IV}Cl where (Cl_2Ph)_3Cor is the trianion of 5,10,15-tri(2,4-dichlorophenyl)corrole. Each metallocorrole was examined as to its catalytic activity for the electoreduction of dioxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO_4. Cyclic voltammetry combined with linear sweep voltammetry at a rotating disk electrode (RDE) and a rotating ring disk electrode (RRDE) was utilized to evaluate the catalytic activity for the …

Matrices From Vegetable Oils, Cashew Nut Shell Liquid, And Other Relevant Systems For Biocomposite Applications, Rafael Quirino, Thomas Garrison, Michael Kessler

Chemistry: Faculty Publications (1990-2023)

The partial replacement of petroleum-derived plastics and composites by novel bio-based materials from inexpensive, renewable, natural resources has the potential to greatly impact the plastics, coatings, and composites industries. Natural starting materials are usually abundant and renewable on a time scale many orders of magnitude smaller than petroleum. These characteristics, in combination with good mechanical properties, make the design of bio-based composites an interesting strategy for lowering the environmental impact of the plastics and composites industries while maintaining economical competitiveness. The present review will focus on the progress made over the last decade in the development of a select group …

Synthesis And Characterization Of New Metallophthalocyanines Containing O_4s_2 Mixed-Donor Substituted Macrocyclic Groups, Meltem Betül Kiliçaslan, Hali̇t Kanteki̇n

Turkish Journal of Chemistry

New phthalocyanine compounds containing mixed-donor substituted macrocyclic groups were synthesized. The complexes of metal phthalocyanines 3--5 were prepared by the reaction of 2 to get dinitrile derivative complexes by means of the corresponding anhydrous metal salts. Structures of the new compounds were characterized by IR, ^1H NMR, ^{13}C NMR, elemental analysis, and MS spectral data.

Time-Dependent Regulation Of Apoptosis By Aen And Bax In Response To 2-Aminoanthracene Dietary Consumption, Worlanyo E. Gato, Dale B. Hales, Stacey R. Mcgee, Jay C. Means

Chemistry: Faculty Publications (1990-2023)

Background/Objective: The modulation of the toxic effects of 2-aminoanthracene (2AA) on the liver by apoptosis was investigated. Fisher-344 (F344) rats were exposed to various concentrations of 2AA for 14 and 28 days. The arylamine 2AA is an aromatic hydrocarbon employed in manufacturing chemicals, dyes, inks, and it is also a curing agent in epoxy resins and polyurethanes. 2AA has been detected in tobacco smoke and cooked foods.

Methods: Analysis of total messenger ribonucleic acid (mRNA) extracts from liver for apoptosis-related gene expression changes in apoptosis enhancing nuclease (AEN), Bcl2-associated X protein (BAX), CASP3, Jun proto-oncogene (JUN), murine double minute-2 p53 …

Light Mediated Drug Delivery Using Photocaged Molecules And Photoswitchable Peptides, Deboleena Mitra

Theses and Dissertations

There are many different types of targeted therapy for cancer treatment. The method of light mediated targeted therapy that we have developed uses photocaged molecules and photoswitchable peptides.

In photocaging, a biologically active molecule is made inactive by the attachment of a photocleavable blocking group. On exposure to UV radiation the photocleavable entity is removed and the biologically active molecule is released. Using this concept we have designed a prodrug that consists of a cell impermeable hydrophilic molecule attached to a photocaged doxorubicin. Upon irradiation with UV light the photosensitive group is removed and cytotoxic doxorubicin is released at the …

Bisbenzylisoquinoline And Hasubanane Alkaloids From Stephania Abyssinica (Dillon & A. Rich) (Menispermeceae), Ruth A. Omole, Jeremiah Gathirwa, Hosea Akala, Hamisi M. Malebo, Alex K. Machocho, Ahmed Hassanali, Isaiah O. Ndiege

All Peer-Reviewed Publications

Two bisbenzylisoquinoline and one hasubanane alkaloids: (-)-pseudocurine (1), (-)-pseudoisocurine (2) and (-)-10-oxoaknadinine (3), were isolated from leaf extract of Stephania abyssinica, a plant used in traditional medicine in South Nyanza region of Kenya. They were characterized using 1D (1H, 13C and DEPT) and 2D (COSY, NOESY, HMQC and HMBC) NMR techniques. (-)-Pseudocurine (1) and (-)-pseudoisocurine (2) exhibited strong to moderate anti-plasmodial activity while (-)-10-oxoaknadinine (3) showed moderate to mild activity. © 2014 Elsevier Ltd. All rights reserved.

Visible Light Mediated Intermolecular [3 + 2] Annulation Of Cyclopropylanilines With Alkynes, Theresa H. Nguyen, Soumitra Maity, Nan Zheng

Chemistry & Biochemistry Faculty Publications and Presentations

Intermolecular [3 + 2] annulation of cyclopropylanilines with alkynes is realized using visible light photoredox catalysis, yielding a variety of cyclic allylic amines in fair to good yields. This method exhibits significant group tolerance particularly with heterocycles. It can also be used to prepare complex heterocycles such as fused indolines.

Evaluating N-Benzylgalactonoamidines As Putative Transition State Analogs For Β-Galactoside Hydrolysis, Qui-Hua Fan, Susanne Striegler, Rebekah Langston, James Barnett

Chemistry & Biochemistry Faculty Publications and Presentations

Experimental evidence is provided for p-methylbenzyl-D-galactonoamidine to function as a true transition state analog for the enzymatic hydrolysis of aryl-β-D-galactopyranosides by β-galactosidase (A. oryzae). The compound exhibits inhibition constants in the low nanomolar concentration range (12–56 nM) for a selection of substrates. Along these lines, a streamlined synthetic method based on phase-transfer catalysis was optimized to afford the required variety of new aryl-β-D-galactopyranosides. Last, the stability of the galactonoamidines under the assay conditions was confirmed.

On-Road Remote Sensing Of Automobile Emissions In The Tulsa Area: Fall 2013, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

The Recession Of 2008 And Its Impact On Light-Duty Vehicle Emissions In Three Western Us Cities, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

The global economic recession of 2008 - 2010 severely depressed light-duty vehicle sales in the United States. On-road fleets observed with a remote vehicle exhaust sensor in 2013 at three historical sampling locations in Denver, Los Angeles and Tulsa showed large reductions in the fleet fractions of 2009 model year vehicles of 40%, 38% and 35% respectively when compared to prerecession 2007 levels with the light-duty truck category suffering the largest percentage declines. The fleet fraction for these ~5 year old vehicles is normally reserved for vehicles more than twice their age. This resulted in a significant increase in the …

Feat Math Ii And A Discussion Of Negative Measurements, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Remote Sensing Of Automobile Emissions In The Denver Area: Winter 2013, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.