Chemistry Commons^™

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 …

Synthesis, Characterization, And Theoretical Studies Of Fluorescent Gumbos And Nanogumbos, Chengfei Lu

LSU Doctoral Dissertations

In this dissertation, novel fluorescent materials, which are referred to as a group of uniform materials based on organic salts (GUMBOS) are synthesized, characterized, and studied for different applications. GUMBOS are solid state organic salts having melting points from 25°C to 250°C. Similar to ionic liquids, GUMBOS are highly tunable and can be designed for specific applications by incorporating multiple-functions into a single ion pair by selection of cation-anion combinations. Chapter 2 is a discussion of the synthesis and characterization of a PEGylated IR786 GUMBOS. These GUMBOS are prepared by a two-step synthesis procedure followed by a facile anion exchange …

“Trans-Positioning” Carbons Within Strained Caged Bicyclic(S): Rom/Rcm (Ring-Opening/Ring-Closing) Metathesis And Dieckmann/Retro-Dieckmann Condensation Routes To A Cis-Decalin Infrastructure, Stefan Malone Cooper Jr

LSU Doctoral Dissertations

This dissertation describes methodology work involving a “Trans-Positioning” motif engaging strategically positioned carbons within a strained bi-carbocyclic core and on a tethered free-dangling hydrocarbon chain ultimately for skeletal rearrangement. Trans-alkenylation and trans-acylation processes are devised for investigation with bicyclo[2.2.2]octyl and bicyclo[2.2.1]heptyl strained cores. Recent advances in olefin metathesis led to an independent proposal of the now applicable, RRM (Ring-Rearranging Metathesis) for trans-alkenylation purposes. A resourceful Dieckmann/retro-Dieckmann sequence is devised for trans-acylation motives. Finally, this dissertation includes atypical diastereoselective reductions and additions which were serendipitously found with trigonal carbon atoms appended to our pertinent strained systems while in pursuit of our …

Synthesis Of Novel C-4 Disubstituted Β-Lactams Through Staudinger Cycloaddition Reaction, Robert Rodriguez, Anjali Nambiar, Ram N. Yadav, Bimal K. Banik

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

Synthesis of novel C-4 disubstituted beta-lactam that has N-methyl pyrrole system has been achieved through Staudinger cycloaddition reaction of acid chloride and imine. Interestingly, this reaction has produced a single stereoisomer.

Structure Vs. Properties Using Chemical Graph Theory, Tabitha N. Williford

College of Graduate Studies: Theses & Dissertations

Chemical graph theory began as a way for mathematicians to bring together the areas of the Physical Sciences and Mathematics. Through its use, mathematicians are able to model chemical systems, predict their properties as well as structure-property relationships. In this dissertation, we consider two questions involving chemical graph theory and its applications. We first look at tree-like polyphenyl systems, which form an important family of compounds in Chemistry, particularly in Material Science. The importance can be seen in LEDs, transmitters, and electronics. In recent years, many extremal results regarding such systems under specific constraints have been reported. More specifically are …

Synthesis, Characterization, And Evaluation Of Novel Bodipy Dyes With Theranostic Applications, Jaime Suzanne Hayes

LSU Doctoral Dissertations

Boron dipyrromethene (BODIPY) dyes, have garnered much attention in recent decades due to their enticing photophysical properties and their bioimaging applicability. Despite the progression of this field, the development of BODIPY based anti-cancer agents and radioimaging dyes has seen little progress. The utilization of fluorescent BODIPYs as photosensitizers for photodynamic therapy, and as boron delivery agents for boron neutron capture therapy offers promise as theranostic agents. Additionally, BODIPY derivatives that absorb and emit in the near-IR regions of the electromagnetic spectrum and bear radioisotopes suitable for radioimaging techniques are of great interest. Chapter 1 is a concise overview of the …

Characterization Of A Water Soluble, Non-Ionic, Helical Poly(Α-Amino Acid), Wayne Huberty

LSU Doctoral Dissertations

A water soluble, non-ionic, rodlike polymer, PEGL, was synthesized and characterized in efforts to synthesize a novel model polymer to study stiff polymers in solution. The rodlike system is likely stiff due to a high relative percent helicity in water up to 50 °C, measured by circular dichroism, the observation of liquid crystalline domains in water, and from the slope measured from conformation plots supplied by GPC/MALS; however, it also apparent the system is aggregating in both a 2 mM azide solution and a buffer (200 mM NaNO3 + 20 mM NaH2PO4 + 2 mM NaN3), in corroboration of negative …

Concern-Driven Integrated Toxicity Testing Strategies For Nanomaterials - Report Of The Nanosafety Cluster Working Group 10, Hugh Byrne, Agnes G. Oomen, Peter M.J. Bos, Teresa F. Fernandes, Kerstin Hund-Rinke, Diana Boraschi, Karin Aschberger, Stefania Gottardo, Frank Von Der Kammer, Dana Kühnel, Danail Hristozov, Antonio Marcomini, Lucia Migliore

Articles

Bringing together topic-related European Union-(EU)-funded projects, the so-called “NanoSafety Cluster” aims at identifying key areas for further research on risk assessment procedures for nanomaterials (NM). The outcome of NanoSafety Cluster Working Group 10, this commentary presents a vision for concern-driven integrated approaches for the (eco-)toxicological testing and assessment (IATA) of NM. Such approaches should start out by determining concerns, i.e. specific information needs for a given NM based on realistic exposure scenarios. Recognized concerns can be addressed in a set of tiers using standardized protocols for NM preparation and testing. Tier 1 includes determining physico-chemical properties, non-testing (e.g. structure …

An Investigation Into Polyiodination Of Activated Benzene Derivatives With Electrophilic Aromatic Substitution Reactions, Dakota Gilbert

Honors Theses

The aim of this research is to investigate the periodination of benzene derivatives that are activated towards electrophilic aromatic substitution. In this research, a successful electrophilic aromatic substitution reaction was completed with procedures that used iodine with silver sulfate as an activating agent in the reaction mixture. The ball-milling technique with N-iodosuccinnimide as the iodinating reagent was also explored. Only one iodine was added onto 4-iodoanisole as the activated benzene derivative. When 2,4-dichloroanisole was the substrate, a small amount of diiodo product accompanied the monoiodo product, but no triiodo (periodinated) product was observed. Nonetheless, the trials of this research give …

Mercury In Fish In North Mississippi Reservoirs: Statistical Analysis And Risk Assessment, Stacy Wolff

Honors Theses

Mercury (Hg) is a pollutant of particular concern because it is wide-spread, persistent, and poses a serious risk to human health. Once released into the atmosphere, it cycles through the environment by a series of complex biogeochemical processes. Upon deposition to aquatic ecosystems, inorganic mercury can be transformed to methylmercury by microorganisms. Methylmercury is a known human neurotoxin that can bioacculmulate in fish tissue and biomagnify up aquatic food chains. Consumption of contaminated fish is the primary route of human exposure to methylmercury. The Mississippi Department of Health has issued fish consumption advisories for Grenada and Enid Lakes in the …

Investigation Into The Synthesis Of Dodecahydro-3a,9a-Diazaperylene, Andrew Palmer

Honors Theses

Dodecahydro-3a,9a-diazaperylene (DHDAP) may serve as a potential donor for use in a donor-sigma-acceptor complex for unimolecular rectification. In order to use DHDAP as a donor, its synthesis must first be studied and altered in such manners as to add a synthetic handle. Other things of important include increasing the yield and better understanding the mechanism by which DHDAP forms. Numerous experiments were conducted in various manners such as testing various solvents among various temperatures to even adding in extra reagents to push the reaction one way or another. In the end the yield of the synthesis was found to improve …

Comparison Of Life Experiences Of Men And Women In The Sciences, Tori Nicole Quist

Honors Program Theses

A lack of sense of belonging and stereotype threat have been shown to contribute to women leaving the sciences (Seymour, 1997; Beasley & Fischer, 2012; Deemer et al., 2013). Contributing to this is the fact that most women find affirmation externally (through friends, family and professors) for their life decisions (Seymour, 1997; Zeldin, 2000). A set of comparative studies in 2000 and 2008 were done examining factors affecting women’s and men’s choices of majors and careers (Zeldin, 2000 and Zeldin, 2008). These studies concluded that men relied on achievements in science as the source of their career decisions to enter …

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.

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 …

Structure-Property Relationships In Polybenzimidazole Materials For Gas Separation And Fuel Cell Applications, Xin Li

Theses and Dissertations

The central theme of my research lies in the investigation of novel polybenzimidazole (PBI)-based materials for different energy related applications ranging from proton exchange membrane fuel cells (PEMFC) to high temperature gas separation. With the aid of a deeper understanding of the structure-property relationships in this class of materials, a better control on PBI chemistry - from monomer structure to polymer morphology to membrane/film processing method was able to be performed in order to achieve greater performance in targeted applications.

In Chapter 1, the overall background of two energy related applications - fuel cells and gas separation was first introduced …

Investigating The Biochemical And Catalytic Properties Of Nitrile Hydratases, Salette Martinez

Dissertations

Chemical and pharmaceutical industries make extensive use of amide compounds for the manufacture of commodity chemicals (e.g., acrylamide) and drug intermediates (e.g., nicotinamide). Production of amide compounds is typically achieved by the hydration of nitrile compounds under acidic or basic conditions, high temperatures, and copper catalysts. However, the use of such chemical methods leads to the generation of unwanted by-products and toxic wastes, in addition to low product yields and high production costs. An alternative route for amide production is the use of a natural catalyst, for example nitrile hydratases (NHase, E.C. 4.2.1.84). NHase is a metalloenzyme that efficiently converts …

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 …

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 …

Rotational Quenching Of H2O By He: Mixed Quantum/Classical Theory And Comparison With Quantum Results, Mikhail V. Ivanov, Marie-Lise Dubernet, Dmitri Babikov

Chemistry Faculty Research and Publications

The mixed quantum/classical theory (MQCT) formulated in the space-fixed reference frame is used to compute quenching cross sections of several rotationally excited states of water molecule by impact of He atom in a broad range of collision energies, and is tested against the full-quantum calculations on the same potential energy surface. In current implementation of MQCT method, there are two major sources of errors: one affects results at energies below 10 cm⁻¹, while the other shows up at energies above 500 cm⁻¹. Namely, when the collision energy E is below the state-to-state transition energy ΔE the …

On Readout Of Vibrational Qubits Using Quantum Beats, Dmytro Shyshlov, Eduardo Berrios, Martin Gruebele, Dmitri Babikov

Chemistry Faculty Research and Publications

Readout of the final states of qubits is a crucial step towards implementing quantum computation in experiment. Although not scalable to large numbers of qubits per molecule, computational studies show that molecular vibrations could provide a significant (factor 2–5 in the literature) increase in the number of qubits compared to two-level systems. In this theoretical work, we explore the process of readout from vibrational qubits in thiophosgene molecule, SCCl₂, using quantum beat oscillations. The quantum beats are measured by first exciting the superposition of the qubit-encoding vibrational states to the electronically excited readout state with variable time-delay pulses. …

Cellulose-Chitosan-Keratin Composite Materials: Synthesis, Immunological And Antibacterial Properties, Meghann Rosewald, Fang Yao Stephen Hou, Tamutsiwa Moven Mututuvari, April L. Harkins, Chieu D. Tran

Chemistry Faculty Research and Publications

Novel composites were synthesized from keratin (KER), cellulose (CEL) and chitosan (CS). The method is recyclable because majority (>88%) of [BMIm⁺Cl^-], an ionic liquid (IL), used as the sole solvent, was recovered for reuse. Experimentally, it was confirmed that unique properties of each component remain intact in the composites, namely bactericide (from KER and CS) and anti-inflammatory property (from KER). Specifically, the composites were examined for their anti-inflammatory influence on macrophages. The cells were imaged and immunophenotyped to determine the quantity using the macrophage marker CD11b. The 75:25 [KER+CS] composite was found to have the …

New Synthetic Strategies For Improved Gas Separation By Nanoporous Organic Polymers, Suha Altarawneh

Theses and Dissertations

Abstract NEW SYNTHETIC STRATEGIES FOR IMPROVED GAS SEPARATION BY NANOPOROUS ORGANIC POLYMERS Suha S. Altarawneh, Ph.D. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of climate change. Therefore, the efficient separation of CO2 from mixtures of gases such as flue gas and impure sources of CH4 (e.g. natural gas and landfill gas) is an essential step in meeting the ever increasing demands on natural gas and creating a cleaner environment. Carbon capture and storage technology (CCS) is one of the methods employed for gas separation using chemisorption and/or physisorption processes. Several materials such as …

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 …

Isomer Dependence In The Assembly And Lability Of Silver(I) Trifluoromethanesulfonate Complexes Of The Heteroditopic Ligands, 2-, 3-, And 4-[Di(1H-Pyrazolyl)Methyl]Phenyl(Di-P-Tolyl)Phosphine, James R. Gardinier, Jeewantha S. Hewage, Sergey V. Lindeman

Chemistry Faculty Research and Publications

Three isomers of a new heteroditopic ligand that contains a di(1H-pyrazolyl)methyl (−CHpz₂) moiety connected to a di(p-tolyl)phosphine group via a para-, meta-, or ortho-phenylene spacer (pL, mL, and oL, respectively) have been synthesized by using a palladium(0)-catalyzed coupling reaction between HP(p-tolyl)₂ and the appropriate isomer of (IC₆H₄)CHpz₂. The 1:1 complexes of silver(I) trifluoromethanesulfonate, Ag(OTf), were prepared to examine the nature of ligand coordination and the type of supramolecular isomer (monomeric, cyclic oligomeric, or polymeric) that would be obtained. …

Synthesis And Spectroscopic Characterization Of High-Spin Mononuclear Iron(Ii) P-Semiquinonate Complexes, Amanda E. Baum, Heaweon Park, Sergey V. Lindeman, Adam T. Fiedler

Chemistry Faculty Research and Publications

Two mononuclear iron(II) p-semiquinonate (pSQ) complexes have been generated via one-electron reduction of precursor complexes containing a substituted 1,4-naphthoquinone ligand. Detailed spectroscopic and computational analysis confirmed the presence of a coordinated pSQ radical ferromagnetically coupled to the high-spin FeII center. The complexes are intended to model electronic interactions between (semi)quinone and iron cofactors in biology.

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 …

Enantiomeric Selective Adsorption Of Amino Acid By Polysaccharide Composite Materials, Simon Duri, Chieu D. Tran

Chemistry Faculty Research and Publications

A composite containing cellulose (CEL) and chitosan (CS) synthesized by a simple and recyclable method by using butylmethylimmidazolium chloride, an ionic liquid, was found to exhibit remarkable enantiomeric selectivity toward the adsorption of amino acids. The highest adsorption capacity and enantiomeric selectivity are exhibited by 100% CS. A racemic amino acid can be enantiomerically resolved by 100% CS in about 96–120 h. Interestingly, adsorption by 50:50 CEL/CS is more similar to that by 100% CS than to 100% CEL. Specifically, whereas 100% CEL has the lowest adsorption capacity and enantiomeric selectivity, 50:50 CEL/CS has sufficient enantiomeric selectivity to enable it …

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 …

Mixed Quantum/Classical Theory For Inelastic Scattering Of Asymmetric-Top-Rotor + Atom In The Body-Fixed Reference Frame And Application To The H2O + He System, Alexander Semenov, Marie-Lise Dubernet, Dmitri Babikov

Chemistry Faculty Research and Publications

The mixed quantum/classical theory (MQCT) for inelastic molecule-atom scattering developed recently [A. Semenov and D. Babikov, J. Chem. Phys.139, 174108 (2013)] is extended to treat a general case of an asymmetric-top-rotor molecule in the body-fixed reference frame. This complements a similar theory formulated in the space-fixed reference-frame [M. Ivanov, M.-L. Dubernet, and D. Babikov, J. Chem. Phys.140, 134301 (2014)]. Here, the goal was to develop an approximate computationally affordable treatment of the rotationally inelastic scattering and apply it to H₂O + He. We found that MQCT is somewhat less accurate at lower scattering energies. For example, below E …