Organic Chemistry Commons^™

Pressure Driven Desalination Membranes: Lyotropic Liquid Crystals Containing Single Walled Carbon, Matteo A. Del Giudice, Samantha Castillo Merigold

Materials Engineering

This project presents a potential alternative desalination technique that utilizes the ion rejection properties of single walled carbon nanotubes dispersed in a lyotropic liquid crystal (LLC) matrix. Previous research has pointed to the polymerizable surfactant methacryloxy ethyl hexadecyl dimethyl ammonium bromide (C16MA) having capabilities of filtering molecular components smaller than a nanometer, when oriented in cylindrical micelles. SWCNTs were dispersed in deionized water by probe sonication and addition of surfactant cetyltrimethylammonium bromide (CTAB) due to SWCNTs’ hydrophobic properties. Membranes were produced containing 55wt% C16MA, 37wt% DI water, 0.1wt% with respect to the monomer (WRM) SWCNTs, 1.9 wt% WRM 2,2-dimethoxy-2-phenylacetophenone (photointiator), …

Biomedical Applications And Syntheses Of Selected Anthraquinone Dyes, Richard Sirard

Senior Honors Theses

Anthraquinones are aromatic organic compounds that have multiple applications in the biomedical field. Some anthraquinone-based compounds are used as fluorophores to contrast cell nuclei while others act as chemotherapeutic agents. However, there are not many fluorescent anthraquinone cell stains currently available. In this study, commercially available anthraquinone dyes, in addition to other dye families and compounds, were reviewed for their unique properties, advantages, and drawbacks. The development and characterization of three novel anthraquinone fluorophores revealed promising photophysical characteristics, like large Stokes shifts. One of the compounds, RBS3, was chosen for fixed and live cell staining and exhibited desirable biomedical properties. …

Nitro Group Reduction For Use In Organic, Cathodic Materials, Brock G. Goeden

Honors Thesis

The industrial demand for higher capacity, light-weight battery materials has skyrocketed in recent years due to heavy investments in portable electronics, electronic vehicles, and renewable energy sources. However, rechargeable battery technology has seen little improvement since the invention of the Lithium-Ion battery in the 1980s. The low energy density of the traditionally utilized LiCoO2 cathodic material (specific capacity: 272 mAh g-1), has limited its potential to meet these increasing demands. To solve this problem, our research group is investigating new types of lightweight, organic, polymeric materials with conductive backbones as a possible replacement for the cathodic materials in Lithium-Ion batteries. …

Discharge Mode Transition In He/Ar Atmospheric Pressure Plasma Jet And Its Inactivation Effect Against Tumor Cells In Vitro, Bolun Pang, Zhijie Liu, Sitao Wang, Yuting Gao, Huaiyan Zhang, Feng Zhang, Xiamin Tantai, Dehui Xu, Dingxin Liu, Michael G. Kong

Bioelectrics Publications

Discharge characteristic comparisons between He and Ar plasma jets have been extensively reported, but is rarely reported for the comprehensive study of discharge mode transition from He jet to Ar jet, especially its induced liquid chemistry and biological effect. In this paper, we investigate the plasma jet mode transformation by varying the Ar contents in the He/Ar mixing working gas, particularly focusing on the effect of liquid chemistry of plasma activated water (PAW) and the corresponding inactivation effect against tumor cells in vitro. The mode transition process from He jet to Ar jet is characterized by the discharge images, …

Energy Renewal: Isothermal Utilization Of Environmental Heat Energy With Asymmetric Structures, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

Through the research presented herein, it is quite clear that there are two thermodynamically distinct types (A and B) of energetic processes naturally occurring on Earth. Type A, such as glycolysis and the tricarboxylic acid cycle, apparently follows the second law well; Type B, as exemplified by the thermotrophic function with transmembrane electrostatically localized protons presented here, does not necessarily have to be constrained by the second law, owing to its special asymmetric function. This study now, for the first time, numerically shows that transmembrane electrostatic proton localization (Type-B process) represents a negative entropy event with a local protonic entropy …

Simulation Studies On The Interactions Of Electron Beam With Wastewater, X. Li, S. Wang, Helmut Baumgart, G. Ciovati, F. Hannon

Electrical & Computer Engineering Faculty Publications

The manufactured chemical pollutants, like 1,4 dioxane and PFAS (per- and polyfluroralkyl substances), found in the underground water and/or drinking water are challenging to be removed or biodegraded. Energetic electrons are capable of mediating and removing them. This paper utilizes FLUKA code to evaluate the beam-wastewater interaction effects with different energy, space and divergence distributions of the electron beam. With 8 MeV average energy, the electron beam exits from a 0.0127 cm thick titanium window, travels through a 4.3 cm distance air and a second 0.0127 cm thick stainless water container window with 2.43 cm radius, and finally is injected …

Catalytic Esterification Of Palm-Based Lauric Acid Diethylene Glycol Via Microwave Heating, Abas Noor Azeerah

Student Works (2020-2029)

Diethylene glycol esters of fatty acids are mixtures of diethylene glycol mono- and di-esters of saturated and unsaturated fatty acids derived from edible oils and fats. The products are produced either by direct esterification of diethylene glycol with fatty acids or by transesterification of diethylene glycol with oils or fats. This study involved in maximizing the conversion of lauric acid to glycol ester via esterification with diethylene glycol, aided by calcined Zn-Mg-Al catalyst in a 250-ml reactor using both conventional and microwave heating. Preliminary catalytic screening involving tin (II) oxalate, Amberlyst-15 and calcined Zn-Mg-Al catalysts in esterification of lauric acid …

Redox-Active Porous Organic Materials For Electrochemical Energy Storage Applications, K. Shamara Weeraratne

Theses and Dissertations

As the demand for renewable energy technologies grows, so does the need for cheaper, more efficient rechargeable batteries to store the energy. While lithium-ion battery (LIBs) technology is well established, it suffers from limited lithium supplies. Furthermore, the highly toxic transition metals used in the electrodes places a huge burden on the environment. Therefore, replacing lithium with more economical sodium metal in rechargeable batteries (i.e. sodium-ion batteries, SIBs) has garnered considerable attention. Despite the fact that sodium and lithium share similar electrochemical properties, which may cause the transition from lithium to sodium easier, the larger ionic radius of Na^{+ …}

Filtration Apparatus Design For Oil-Water Separation Using Membranes And Sponges, Alec Jerger

Williams Honors College, Honors Research Projects

It can be difficult to separate water and oil emulsions through traditional filtration. Therefore, investigations of filtering using thermo-responsive (TR) polymers, in this case poly(vinyl methyl ether) (PVME), was conducted. It’s hypothesized that below its lower critical solution temperature (LCST), PVME has an affinity for water while oil substances do not. Above the LCST the opposite will be true. To verify this hypothesis, iterations of filtration designs were created to provide optimum control over the parameters to measure flow. The final optimized experimental apparatus was a Chromaflex glass column which was air tight and controlled all parameters besides fluid flow. …

Effects Of Hole Transporting Layers And Surface Ligands On Interface Energetics And Photovoltaic Performance Of Methylammonium Lead Iodide Perovskites, So Min Park

Theses and Dissertations--Chemical and Materials Engineering

Organic metal halide perovskites are promising materials for various optoelectronic device applications such as light emitting diodes (LED) and photovoltaic (PV) cells. Perovskite solar cells (PSCs) have shown dramatic increases in power conversion efficiency over the previous ten years, far exceeding the rate of improvement of all other PV technologies. PSCs have attracted significant attention due to their strong absorbance throughout the visible region, high charge carrier mobilities, color tunability, and ability to make ultralight weight devices. However, organic metal halide perovskites still face several challenges. For example, their environmental stability issue must be overcome to enable widespread commercialization. Meeting …

A Theoretical And Experimental Study Of Charge Transport In Organic Thermoelectric Materials And Charge Transfer States In Organic Photovoltaics, Ashkan Abtahi

Theses and Dissertations--Physics and Astronomy

Applications of organic electronics have increased significantly over the past two decades. Organic semiconductors (OSC) can be used in mechanically flexible devices with potentially lower cost of fabrication than their inorganic counterparts, yet in many cases organic semiconductor-based devices suffer from lower performance and stability. Investigating the doping mechanism, charge transport, and charge transfer in such materials will allow us to address the parameters that limit performance and potentially resolve them. In this dissertation, organic materials are used in three different device structures to investigate charge transport and charge transfer. Chemically doped π-conjugated polymers are promising materials to be used …

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

Visualizing The Fate And Distribution Of Pahs In Spartina And Avicennia Tissues From Barataria Basin, La, Kristina Jeannette Sebastian

LSU Master's Theses

During crude oil spill events, vegetation in marsh environments sequester polycyclic aromatic hydrocarbons (PAHs) from the crude oil by partitioning from the air phase through the waxy cuticle on the leaf surface. Recent studies from Macondo oil-impacted marshes have demonstrated that cycling of low molecular weight petrogenic PAHs occurs through the cuticle and other leaf tissue. At present, our understanding of how PAHs travel through the cuticle is coarse and limited by grab samples across the entire leaf, which preventing a full understanding the dynamics of PAH cycling in this environment. Multiphoton (MP) confocal microscopy visualizes the distribution of PAHs …

The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O₂(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O₂(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. …

Multidimensional Mass Spectrometry Of Chemonic™ Ccg-6 Nonionic Surfactant With Separation By Polarity And Shape, Charles Johnson

Williams Honors College, Honors Research Projects

Chemonic™ CCG-6 surfactant is a water-soluble poly(ethylene glycol) (PEG) conjugated alkyl glyceride emollient. This surfactant exists as a complex mixture of a glycerol cores conjugated with poly(ethylene glycol) branches (PEGylation) that were partially esterified with caprylic (C8) and capric (C10) acids. These may be esterified on one, two, or all three arms of the glyceride. The architecture of the structures in this mixture was studied using multidimensional mass spectrometry (MS). Mass spectrometry was interfaced with ultra-performance liquid chromatography (UPLC) and ion mobility (IM) separation. The mixture was separated by reversed-phase LC, oligomers of the star-branched polymer were separated according to …

Oxidative Degradation Of Lignin And Investigation Of Utilization Of Lignin-Derived Materials As Building Blocks For Epoxy Resins, Zhen Fang

Theses and Dissertations--Chemistry

Lignin, the second most abundant biopolymer on earth, is potentially a replaceable source for bulky fuels and chemical feedstocks. There have been numerous reports on methods for the oxidative cleavage of β-O-4 linkages but relatively few reports of how those methods affect other linkages that are present in lignin. We investigated how the β-1 and β-5 linkages respond under oxidative conditions proposed for lignin deconstruction based on their effect on β-O-4 linkages. Mechanochemical treatment of lignin can greatly improve the yield of monomer products and we applied a mechanochemical approach, using powerful ring-and-puck milling to promote lignin degradation. Along with …

Development And Thermodynamic Analysis Of An Integrated Mild/Partial Gasification Combined Cycle (Impgc) Under Green And Brown Field Conditions With And Without Carbon Capture, Henry A. Long Iii

LSU New Orleans Theses and Dissertations

Coal is a very prominent energy source in the world, but it is environmentally unattractive due to its high sulfur and ash content as well as its alleged contribution towards climate change, but it is affordable, abundant, and has high energy content. Thus, utilizing coal in a cleaner and more efficient way has become necessary. One promising clean coal technology involves fully gasifying coal into synthesis gas, cleaning it, and feeding it into a high-efficiency combined cycle, such as an Integrated Gasification Combined Cycle (IGCC). Inspired by the recent success of warn gas cleanup (WGCU), mild and partial gasification are …

Micro-Flow Nanocatalysis: Synergic Effect Of Tfoh@Spions And Micro-Flow Technology As An Efficient And Robust Catalytic System For The Synthesis Of Plasticizers, Maryam Tashi, Behnaz Shafiee, Yoshie Sakamaki, Ji-Yun Hu, Zachary Heidrick, Ahmad R. Khosropour, M. Hassan Beyzavi

Chemistry & Biochemistry Faculty Publications and Presentations

The combination of continuous flow technology with immobilizing of only 0.13 mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h−1 compared to 403.8 to 3099 h−1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.

Thienoisatin Oligomers As N-Type Molecular Semiconductors, Natalie M. Kadlubowski, Xuyi Luo, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

Organic field effect transistors (OFETs) offer many advantages compared to traditional inorganic transistors, such as flexibility and solution processability. In this study we design and synthesize two thienoisatin-based organic semiconducting small molecules, then investigate their electronic properties in n-type OFETs. To introduce n-type charge transport, electron-withdrawing dicarbonitrile moieties were installed on thienoisoindigo and bis-thienoisatin molecules, which led to a quinoidal conjugation on thienoisoindigo, while maintaining an aromatic conjugation on the bis-thienoisatin. Following the syntheses, the molecules were characterized to determine highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels via cyclic voltammetry, as well as any potential …

Oxidation Of N-Doped Multiwalled Carbon Nanotubes And Formation Of Discontinuous Spiraled Carbon Nanoribbons, Aman Preet Kaur, Mark S. Meier, Rodney Andrews, Dali Qian

Chemistry Faculty Publications

The effects of five commonly used wet chemical oxidations were studied for the extent of oxidation of graphitized nitrogen-doped multiwalled carbon nanotubes (N-MWCNTs). KMnO₄/ H₂SO₄ was the most potent oxidant, as it produced the highest fraction of oxygen-containing functional groups. Electron microscopy studies showed that the treatment of annealed N-MWCNTs (G-N-MWCNTs) with H₂SO₄/HNO₃ and H₂SO₄/KMnO₄ mixtures leads to interesting spiraled ribbon textures. A structural model, involving the stacking of coiled subunits to form a discontinuous carbon nanoribbon rather than a continuous ribbon is proposed to …

Highly Flame Retardant And Bio-Based Rigid Polyurethane Foams Derived From Orange Peel Oil, Chunyang Zhang

Electronic Theses & Dissertations

Polyurethane is an important class of polymer which is being used for various industrial applications in the form of rigid foams, flexible foams, thermoplastic, elastomer, coating, and adhesive. Especially there is a huge market for rigid polyurethane foams for their applications as thermal insulating material in building and housing. In general, polyurethanes are prepared using polyols and diisocyanates. Most of the polyols used by industries are petrochemical based. In this project, a novel polyol from an orange peel oil-based derivative, limonene dimercaptan, was synthesized using one step photochemical thiol-ene reaction. The synthesized polyol was used to prepare flame retardant polyurethane …

Investigation Of Volatile Organic Compounds (Vocs) Detected At Vapor Intrusion Sites, Mohammadyousef Roghani

Theses and Dissertations--Civil Engineering

This dissertation investigates unexplained vapor intrusion field data sets that have been observed at hazardous waste sites, including: 1) non-linear soil gas concentration trends between the VOC source (i.e. contaminated groundwater plume) and the ground surface; and, 2) alternative pathways that serve as entry points for vapors to infiltrate into buildings and serve to increase VOC exposure risks as compared to the classic vapor intrusion model, which primarily considered foundation cracks as the route for vapor entry. The overall hypothesis of this research is that theoretical knowledge of fate and transport processes can be systematically applied to vapor intrusion field …

Effect Of Curing Rate On The Microstructure And Macroscopic Properties Of Epoxy Fiberglass Composites, Ammar Patel, Olesksandr Kravchenko, Ica Manas-Zloczower

Mechanical & Aerospace Engineering Faculty Publications

Curing rates of an epoxy amine system were varied via different curing cycles, and glass-fiber epoxy composites were prepared using the same protocol, with the aim of investigating the correlation between microstructure and composite properties. It was found that the fast curing cycle resulted in a non-homogenous network, with a larger percentage of a softer phase. Homogenized composite properties, namely storage modulus and quasi-static intra-laminar shear strength, remained unaffected by the change in resin microstructure. However, fatigue tests revealed a significant reduction in fatigue life for composites cured at fast curing rates, while composites with curing cycles that allowed a …

The Role Of Catalytic Residue PKA On The Hydrolysis/Transglycosylation Partition In Family 3 Β-Glucosidases, Inacrist Geronimo, Christina M. Payne, Mats Sandgren

Chemical and Materials Engineering Faculty Publications

β-Glucosidases (βgls) primarily catalyze the hydrolysis of the terminal glycosidic bond at the non-reducing end of β-glucosides, although glycosidic bond synthesis (called transglycosylation) can also occur in the presence of another acceptor. In the final reaction step, the glucose product or another substrate competes with water for transfer to the glycosyl-enzyme intermediate. The factors governing the balance between the two pathways are not fully known; however, the involvement of ionizable residues in binding and catalysis suggests that their pK_a may play a role. Through constant pH molecular dynamics simulations of a glycoside hydrolase Family 3 (GH3) βgl, we …

Layer-By-Layer Assembled Membranes With Immobilized Porins, Sebastián Hernández, Cassandra Porter, Xinyi Zhang, Yinan Wei, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

New and advanced opportunities are arising for the synthesis and functionalization of membranes with selective separation, reactivity, and stimuli-responsive behavior. One such advancement is the integration of bio-based channels in membrane technologies. By a layer-by-layer (LbL) assembly of polyelectrolytes, outer membrane protein F trimers (OmpF) or “porins” from Escherichia coli with central pores ∼2 nm in diameter at their opening and ∼0.7 × 1.1 nm at their constricted region are immobilized within the pores of poly(vinylidene fluoride) microfiltration membranes, in contrast to traditional ruptured lipid bilayer or vesicle processes. These OmpF-membranes demonstrate selective rejection of non-charged organics over ionic solutes, …

Oxidation Of Substituted Catechols At The Air-Water Interface: Production Of Carboxylic Acids, Quinones, And Polyphenols, Elizabeth A. Pillar, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic activities contribute benzene, toluene, and anisole to the environment, which in the atmosphere are converted into the respective phenols, cresols, and methoxyphenols by fast gas-phase reaction with hydroxyl radicals (HO(•)). Further processing of the latter species by HO(•) decreases their vapor pressure as a second hydroxyl group is incorporated to accelerate their oxidative aging at interfaces and in aqueous particles. This work shows how catechol, pyrogallol, 3-methylcatechol, 4-methylcatechol, and 3-methoxycatechol (all proxies for oxygenated aromatics derived from benzene, toluene, and anisole) react at the air-water interface with increasing O3(g) during τc ≈ 1 μs contact time and contrasts their …

An Expedited, Regiospecific Para-Bromination Of Activated Aryls, Kathryn E. Dudley

Masters Theses & Specialist Projects

Electrophilic Aromatic Substitution (EAS) is one of the most frequently used aryl substitution methods. Aside from the fact that most EAS reactions require an acid and an oxidizer to proceed, the reactions involving activated aryls typically produce a mixture of ortho- and para- products as well as an ortho-/para- disubstituted product. Regiospecificity in aromatic substitution is key in the production of many compounds in a variety of disciplines. Since EAS is one of the most often used substitution methods, it is extremely important to develop an efficient method for regiospecific substitutions. Previous research developed a method of ortho-substitution by using …

Acenes, Heteroacenes And Analogous Molecules For Organic Photovoltaic And Field Effect Transistor Applications, Devin B. Granger

Theses and Dissertations--Chemistry

Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have …

Preparation And Application Of Catalysts For The Stereospecific Reduction And Photooxygenation Of Olefins In Continuous Operations: A Novel Method For The Production Of Artemisinin, Daniel C. Fisher

Theses and Dissertations

Over the last two centuries, the discovery and application of catalysts has had a substantial impact on how and what chemicals are produced.Given their broad significance, our group has focused on developing new catalyst systems that are recoverable and reusable, in an attempt to reduce concomitant costs.

Our efforts have centered on constructing a recyclable chiral heterogeneous catalyst capable of effecting asymmetric hydrogenations of olefins with high stereoselectivity. A class of phosphinoimidazoline ligands, developed by researchers at Boehringer-Ingelheim, known as BIPI ligands, have proven efficacious in the asymmetric reduction of alkenes. However, these chiral ligands are homogeneous and coordinated to …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …