Analytical Chemistry Commons^™

The Influence Of Ion-Ion Correlations On Conductivity In Concentrated Ionic Systems, Md Dipu Ahmed

Masters Theses

This study delves into the fascinating realm of concentrated ionic systems, such as ionic liquids, superionic materials, organic ionic plastic crystals, and polyelectrolytes, which hold immense potential for energy storage applications. The focus is on understanding the intricate role of ionic correlations in shaping their ionic conductivity behavior. These correlations can either boost or impede conductivity, yet their underlying mechanisms remain elusive. Through extensive investigation of various materials, including ionic liquids with differing anionic masses, pure organic ionic plastic crystals, and doped systems, this research employs advanced techniques like dielectric spectroscopy and innovative momentum conservation models to quantify these correlations. …

Reactive Chemistries For Protein Labeling, Degradation, And Stimuli Responsive Delivery, Myrat Kurbanov

Doctoral Dissertations

Reactive chemistries for protein chemical modification play an instrumental role in chemical biology, proteomics, and therapeutics. Depending on the application, the selectivity of these modifications can range from precise modification of an amino acid sequence by genetic manipulation of protein expression machinery to a stochastic modification of lysine residues on the protein surface. Ligand-Directed (LD) chemistry is one of the few methods for targeted modification of endogenous proteins without genetic engineering. However, current LD strategies are limited by stringent amino acid selectivity. To bridge this gap, this thesis focuses on the development of highly reactive LD Triggerable Michael Acceptors (LD-TMAcs) …

New Alkyd Resins From Underutilized Indigenous Seed Oils: Synthesis And Characterization, Aliru O. Mustapha, Hakeem B. Ayoku, Halimah A. Amao

Karbala International Journal of Modern Science

The underutilization of sesame (Sesamum indicum L.), sweet almond (Prunus amygdalus), and jatropha (Jatropha curcas) seeds indicates a significant resource waste. Nine different varieties of 25% (short), 40% (medium), and 60% (long) alkyd resins were produced from the cross-section of drying, semi-drying, and non-drying oils. A large amount of conversion occurred, with the extent of the reaction (Pav) decreasing as time progressed and the corresponding increase in alkyds' average degree of polymerization (Dp) showing synthesized alkyds. Surface drying from the set-to-dry and dry-through periods climaxed at 2 hours for all the alkyds. Except for alkali, synthesized alkyd resins demonstrated outstanding …

Application Of Mass Spectrometry For The Characterization Of Synthetic Oligomers And Natural Lignin, Poorya Kamali

Theses and Dissertations--Chemistry

As part of the ongoing effort to substitute finite fuel and chemical resources with renewable ones, biomass is emerging as one of the most promising sources. Biomass consists of three main components of cellulose, hemicellulose, and lignin. Traditionally, cellulose has been used extensively in pulping industry, while lignin has been considered waste and is burned to generate heat. Lignin, a complex aromatic polymer component of biomass, has the potential to be used as a source of aromatic chemicals and pharmaceutical synthons. The recalcitrant nature of lignin, the lack of effective lignin breakdown methods and analytical techniques to analyze it are …

Intracellular Delivery Of Therapeutic Biomolecules Through Versatile Polymer Nanotechnology, David C. Luther

Doctoral Dissertations

Advancing pharmaceutical technology has made it possible to treat diseases once considered ‘undruggable.’ Access to these new pharmaceutical targets is possible thanks to the advent of protein and nucleic acid therapeutics. Responses to the COVID-19 pandemic, as well as cutting-edge treatments for cancer and multiple sclerosis have centered on these biologic therapies, promising even greater value in the future. However, their utility is limited at a cellular level by inability to cross the plasma membrane. Nanocarrier technologies encapsulate therapeutics and facilitate uptake into the cell but are often trapped and degraded in endosomes. Arginine-functionalized gold nanoparticles (Arg-NPs) provide efficient, direct …

Biomaterials: From Scaffold Design To Implant Optimization, Jennifer Marie Armen

Electronic Theses and Dissertations

This work encompasses three individual projects concerning biomaterials and their modifications. Chemically-Induced Cross-Linking of Peptidic Fibrils for Scaffolding Polymeric Particles and Macrophages EAK16-II (EAK) is a self-assembling peptide (SAP) that forms β-sheets and βfibrils through ionic-complementary interactions at physiological ionic strengths. The soft materials can be injected in vivo, creating depots of drugs and cells for rendering pharmacological and biological actions. The scope of the applications of EAK is sought to extend to tissues through which the flow of extracellular fluid tends to be limited. In such anatomical locales the rate and extent of the fibrilization are limited insofar as …

Nitro-Aromatic Polymers For Conversion-Style Battery Cathodic Materials, Brady P. Samuelson

Honors Thesis

The development of organic electrode materials in rechargeable batteries has seen a resurgence in recent decades. This spike in interest is mostly due to the increased investments in renewable energy sources, grid-scale energy storage, and the rapid transition to electric vehicles. Current lithium battery cathode materials typically use some form of lithium metal oxide (specific capacity: 272 mAh g^-1 which has problems with limited capacity, thermal runaway, and an unreliable supply chain. Our research group’s solution involves investigating new lightweight, organic redox groups combined with a conductive polymer backbone to serve as a possible replacement for the cathode in …

Analysis Of The Light Responsive Azobenzene Peptide Nucleic Acid Duplexes, Kat Nguyen

Honors College Theses

Peptide nucleic acids (PNAs) are oligonucleotide analogues in which the sugar-phosphate backbone has been replaced by a pseudopeptide skeleton. Since PNAs use the natural nucleobases (Adenine, Thymine, Cytosine, Uracil, and Guanine) found in either DNA and/or RNA, they are able to hybridize according to Watson-Crick base-pairing to form duplexes. PNA is a promising therapeutic agent because they can function as antigene or antisense chemical agents. To further enhance their utility, we aim to incorporate a photoswitchable moiety using azobenzene. Here, we report the results of the synthesis and purification of a photoswitchable 11 mer PNA along with initial characterization efforts.

Immobilized-Enzyme Reactors Integrated Into Analytical Platforms: Recent Advances And Challenges, Bert Wouters Dr, Sinead Currivan, Noor Abdulhussain, T. Hankemeier, Peter J. Schoenmakers

Articles

Immobilized-enzyme reactors (IMERs) are flow-through devices containing enzymes that are physically confined or localized with retention of their catalytic activities. IMERs can be used repeatedly and continuously and have been applied for (bio)polymer degradation, proteomics, biomarker discovery, inhibitor screening, and detection. Online integration of IMERs with analytical instrumentation, such as high-performance liquid chromatography (HPLC) systems, reduces the time needed for multi-step workflows, reduces the need for sample handling, and enables automation. However, online integration can also be challenging, as reaching its full potential requires complex instrumental setups and experienced users. This review aims to provide an assessment of recent advances …

Characterization Techniques And Cation Exchange Membrane For Non-Aqueous Redox Flow Battery, Kun Lou

Doctoral Dissertations

The motivation of this work comes from one of the major problems of emerging non-aqueous flow battery (NAFB) that a separator or membrane which facilitates conductivity and blocks redox species crossover does not exist. Although many aspects of principles can be mirrored from mature fuel cell and aqueous flow battery, it is found that some well-defined membrane properties in aqueous systems such as swelling, transport and interactions are different in non-aqueous solvents to some extent. However, the approach of this work does follow the way perfluorosulfonate ion exchange membrane (PFSA) facilitated development of fuel cell and aqueous flow battery in …

Doping Of Conjugated Polymers: Preparation, Characterization And Device Fabrication, Kan Tang

Dissertations

Semiconducting conjugated polymers (CPs) as emerging materials for advanced electronic applications such as sensors, OPVs, and OEFTs has become an intriguing research topic in the past decades. It opens a new avenue of “flexible” electronics, which has shown great potential in next-generation electronic devices.

However, due to the nature of CP materials and related solution processing techniques, unlike almost perfectly crystalline silicon materials, CPs in the solid-state often exhibit much lower crystallinity if it is not complete amorphous, which severely hinder the electronic property and optical property of the materials. The crystallinity of CPs in a film is often uniquely …

Degumming Of Hemp Fibers Using Combined Microwave Energy And Deep Eutectic Solvent, Bulbul Ahmed

LSU Master's Theses

Hemp is considered as one of the sustainable agricultural fiber materials. Degumming or surface modification of hemp bast is needed to produce single fibers for ensuing textile and industrial applications. The traditional degumming process necessitates a high amount of alkali, which causes detrimental environmental pollution. This study offers a new method to degum hemp fibers with reduced use of harmful alkali and precious water resources. In this work, hemp bast fibers were degummed by using combined microwave energy and deep eutectic solvent (DES). The properties of hemp fibers manufactured by this method were investigated and compared with the traditional alkali …

A Conductivity Analysis Of A Newly Synthesized Poly(Ethylene Glycol) Methyl Ether Hydroxide Electrolyte, Sarah Marie Peterson

Honors Theses

This thesis investigates the synthesis and conductive properties of a Poly (ethylene glycol) methyl ether-based polymer electrolyte. The goal of the synthesis is to enhance the hydroxide ion conduction properties of the polymer with its cationic groups attached. The MePEG backbone contained seven ethylene glycol groups and was modified to substitute the hydroxide group in the MePEG with trimethylamine. In addition, the bromide added in the synthesis was exchanged for hydroxide ions to allow for the transportation of hydroxide ions in polymeric electrolytes that can be used in Anion Exchange Membrane Fuel Cells. The newly synthesized polymer was compared to …

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. …

Development Of Engineered Soil Surrogates For Modeling Natural Soil Sorption Behavior, Ghada Yehia Abdalla

LSU Doctoral Dissertations

The land produces more than 95% of the global food supply, and with a continuously growing population, we need to optimize the use of the available agricultural land. Soil organic matter (SOM) is an essential component of soils, especially concerning their fertility and sorption behavior. The chemical composition of the SOM consists of lipids, lignin, and cellulose. However, the heterogeneous and complex nature of SOM, and real soils, makes their study challenging and introduces uncontrollable factors.

Therefore, structural mimics of natural soils with increasing complexity representing the real soil functionality were synthesized and evaluated for bulk properties related to their …

Valorization Of Xylan In Agroforestry Waste Streams, Harrison Appiah

Graduate Theses, Dissertations, and Problem Reports

Valorization of Xylan in Agroforestry Waste Streams.

Harrison Appiah

Microwave-assisted deep eutectic solvent and gamma-valerolactone metallic chloride catalyzed conversion of xylan to furfural were investigated using a 2x3 factorial experimental design at two levels of percent microwave power, reaction time, and catalyst concentration. The levels of each factor studied were (20%, 60% microwave power, 2, 4 minutes, and 10, 20mg) respectively. The effect of three metallic chloride catalysts (LiCl, FeCl3.6H20, CuCl2) on the conversion of xylan to furfural was also investigated. The gamma-valerolactone-ferric chloride sent system exhibited the highest mean yield of furfural (56.50%). The next highest furfural yield of …

Functionalized Materials From Atom Transfer Radical Processes, Sean Fischer

Electronic Theses and Dissertations

This work is focused on the synthesis, characterization, and application of functionalized materials prepared from atom transfer radical processes. Atom transfer radical processes encompass both atom transfer radical addition (ATRA) and polymerization (ATRP) reactions, both of which are catalyzed by ppm amounts of copper complexes. The synthetic efforts of ATRA include increasing adduct selectivity through optimization of reaction conditions to generate small molecules in high to moderate yields. ATRA provides retention of the halogen moiety, which is an attractive functional group that can be further modified with other transformations. Specifically, the copper-catalyzed azide-alkyne [3+2] cycloaddition (CuAAC) allows for the realization …

Structure And Dynamics Of Phospholipid Vesicles And The Dependence On Nanoscale Interactions With Molecules Of Varying Complexity, Lakshapathy Widanelage Judith Upeka De Mel

LSU Doctoral Dissertations

In this dissertation, molecular interactions and changes imposed by nano-scale structures on phospholipid vesicles were investigated. 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) large unilamellar vesicles (LUVs) were used as the model system. Understanding changes of the bilayer structure, interfacial properties, lipid dynamics, and self-assembly, allows bridging relationships between biological cell membrane structure and dynamics to cellular functionalities. For example, membrane curvature changes are linked to membrane protein functions, although the exact mechanisms of control are not yet understood. Moreover, the knowledge gained from vesicle models allows exploring novel strategies for drug delivery applications. To achieve this, DOPC LUVs were synthesized and characterized by a …

Visualization Without Vision – How Blind And Visually Impaired Students And Researchers Engage With Molecular Structures, Croix J. Laconsay, Henry B. Wedler, Dean J. Tantillo

Journal of Science Education for Students with Disabilities

This article examines the tools and techniques currently available that enable blind and visually impaired (BVI) individuals to visualize three-dimensional objects used in learning chemistry concepts. How BVI individuals engage with and visualize molecular structure is discussed and recent tactile (or haptic) and auditory methods for visualization of various chemistry concepts are summarized. Remaining challenges for chemistry education researchers are described with the aim of highlighting the potential value of educational research in further enabling BVI students to pursue careers in science, technology, engineering, and mathematics (STEM) fields.

Thiophene Derivative Monomers Co-Electropolymerized On Microelectrodes Within Arrays For Tailored Surface Chemistry And Electrochemical Properties, Benjamin J. Jones

Graduate Theses and Dissertations

Potentiodynamic co-electropolymerization of two thiophene derivatives, (2,3-dihydrothieno[3,4-b]dioxin-2-yl)methanol (1) and 4-((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)-methoxy)-4-oxobutanoic acid (2), in aqueous solutions (0.02 M total monomer, 0.05 M sodium dodecyl sulfate (SDS) and 0.1 M LiClO4) on gold microband electrodes in an array was investigated. A modified Steglich esterification reaction between monomer 1 and succinic anhydride produced monomer 2 at 93.6% yield. Seven deposition solutions of the two monomers, defined by mol% of monomer 2 (0, 25, 34, 50, 66, 75, 100) generated seven sets of polymer films by cyclic voltammetry in a specially designed cell to conserve monomer. The onset potential for monomer oxidation and total …

Effect Of Post-Consumer Content And Bioplastic Incorporation On Polymeric Resin In Consumer Applications, Shelby Bicknell

Electronic Theses & Dissertations

Controversy surrounds the use of plastic products, primarily due to their potentially negative impact on the environment at the end of their lifecycle. The most widely used plastics are manufactured from petrochemicals such as petroleum, coal or natural gas. Petrochemical plastics are not able to readily breakdown in the environment, which aggravates the existing pollution problems. Fortunately, there are eco-friendly alternatives to petrochemical-based plastics. Bioplastics may be derived from renewable sources, biodegradable, or both. Bio-based plastics are plastics that may be derived from renewable biomass sources including, but not limited to, vegetable oils, cornstarch, straw, woodchips, and food waste. They …

Fabrication Of Polymer Monoliths Within The Confines Of Non-Transparent 3d-Printed Polymer Housings, Noor Abdulhussain, Suhas H. Nawada, Sinéad Currivan, Marta Passamonti, Peter J. Schoenmakers

Articles

In the last decade, 3D-printing has emerged as a promising enabling technology in the field of analytical chemistry. Fused-deposition modelling (FDM) is a popular, low-cost and widely accessible technique. In this study, RPLC separations are achieved by in-situ fabrication of porous polymer monoliths, directly within the 3D-printed channels. Thermal polymerization was employed for the fabrication of monolithic columns in optically non-transparent column housings, 3D-printed using two different polypropylene materials. Both acrylate-based and polystyrene-based monoliths were created. Two approaches were used for monolith fabrication, viz. (i) in standard polypropylene (PP) a two-step process was developed, with a radical initiated wall-modification step …

The Synthesis Of A Mepeg-Based Hydroxide Conducting Electrolyte And The Optimization Of The Mepeg-Tosylation Reaction, Andrew Ladner

Honors Theses

As society is becoming increasingly aware of the effects of climate change and the ever-looming threat of a fuel shortage, exploring green and renewable alternative energy production, such as fuel cells, is paramount. This project investigates the synthesis of a polyethylene glycol monomethyl ether (MePEG_n) based polymer as well as the optimization of the MePEG Tosylation reaction. The MePEG explored contains seven polymerized ethoxy groups (MePEG₇). The MePEG₇ polymer was modified by substituting a positively-charged trimethylamine group in the place of the alcohol functional group at the end of the PEG chain. The reason for …

Polysaccharide And Silver Nanoparticles Based Hydrogels, Porous Materials, And Sensors, Muhammad R. Hossen

Electronic Theses and Dissertations

Cellulose based hydrogels and porous materials are gaining significant attention across a wide range of applications due to the natural abundance, biodegradability and physicochemical tunability of this polysaccharide. Cellulose nanofibrils (CNF) outperform cellulose fibers in terms of physicochemical tunability since CNF possess relatively high surface area. However, superior dispersibility of CNF in aqueous phase makes it challenging for traditional methods to dewater CNF suspensions to fabricate robust hydrogels and porous materials. In this dissertation, a novel scalable capillary based method to dewater CNF suspensions is invented as well as CNF hydrogels and porous materials with a broad range of porosity …

Hypervalent Iodine Compounds With Carboxylate And Tetrazolate Ligands, Avichal Vaish

Chemistry Theses and Dissertations

In modern organic chemistry, hypervalent (HV) iodine(III) compounds are frequently used as oxidizing agents but application of λ³-iodanes in polymer and material chemistry is still underexplored. This dissertation describes the preparation of dynamic and self-healing materials by employing ligand exchange reactions involving HV iodine(III) compounds of the type ArIL₂ (Ar = Aryl, L = ligand, e.g., carboxylate or (pseudo)halide). These compounds can undergo ligand exchange reactions in presence of nucleophiles (Nu^-) to form ArINu₂. Diacetoxyiodo benzene was successfully employed as a crosslinker to prepare dynamic and self-healing gels derived from carboxylate-containing polymers. Furthermore, …

Protein Detection And Structural Characterization By Mass Spectrometry Using Supramolecular Assemblies And Small Molecules, Bo Zhao

Doctoral Dissertations

Mass spectrometry (MS) has played an increasingly prominent role in proteomics and structure biology because it shows superior capabilities in identification, quantification and structural characterization of proteins. To realize its full potential in protein analysis, significant progress has been made in developing innovative techniques and reagents that can couple to MS detection. This dissertation demonstrates the use of polymeric supramolecular assemblies for enhanced protein detection in complex biological mixtures by MS. An amphiphilic random co-polymer scaffold is developed to form functional supramolecular assemblies for protein/ peptide enrichment. The influences of charge density and functional group pK_a on host-guest interactions …

Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland

Electronic Thesis and Dissertation Repository

Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was …

Modification And Optimization Of Conducting Polymer-Modified, Redox-Magnetohydrodynamics (R-Mhd) Pumping For Enhanced And Sustained Microfluidics Applications, Md Foysal Zahid Khan

Graduate Theses and Dissertations

In this work, a novel microfluidic pumping approach, redox-magnetohydrodynamics (R-MHD) has improved by materials and device optimization to use in lab-on-a-chip applications. In R-MHD, magnetic flux (B) and ionic current density (j) interacts to generate body force (FB) in between active electrodes, according to the equation FB = j×B. This unique fluid pumping approach is scalable, tunable, generates flat flow profile, and does not require any channels or valves. Pumping performance, such as speed scales with the ionic current density (j) and duration depends on the total charge (Q). The ionic current density (j) results from the conversion of electronic …

Enhanced Mass Spectrometric Analysis Of Peptides And Proteins Using Polymeric Reverse Micelles, Mahalia Adelina Corazon Paningbatan Serrano

Doctoral Dissertations

Mass spectrometry (MS) has become a key and indispensable tool in the identification, characterization, and quantitative analysis of proteins owing to its universality, sensitivity, specificity, and its capability for multiplexed detection. Because biological samples containing these protein analytes are almost always complex systems, various techniques are employed in conjunction with MS to fully harness its analytical potential and enhance its detection capabilities. This dissertation explores the use of amphiphilic polymeric reverse micelles in enriching proteins and peptides from complex biological mixtures and in enhancing their mass spectrometric analysis. Fundamental studies that elucidate the molecular basis for the observed MS signal …

Voc Emission Factors From 3d Printers - Abs (Acrylonitrile-Butadiene-Styrene) Type Filaments, Dean Lay

LSU Master's Theses

Acrylonitrile-butadiene-styrene (ABS) is a polymer that is widely used in many plastic products and is receiving new attention due to its use as a filament for fused deposition modelling (FDM) 3D printers. It has been shown to emit potentially dangerous volatile organic compounds (VOCs) when heated at temperatures used in the 3D printing process. Many new products are becoming available that contain various additives to the polymer matrix, which have an unknown effect on the emission profiles and rates. In this study a method is developed using a modified system for thermal diagnostic studies (STDS) to evaluate VOC emission from …