Chemistry Commons^™

Probing The Surface Acidity Of Supported Aluminum Bromide Catalysts, Md Ashraful Abedin, Swarom Kanitkar, Nitin Kumar, Zi Wang, Kunlun Ding, Graham Hutchings, James J. Spivey

Faculty Publications

Solid acid catalysis is an important class of reactions. The principal advantages of solid acid catalysts as compared to their corresponding fluid acids include minimal waste and ease of product separation. One type of these catalysts is based on aluminum bromide (Al2Br6), which is a stronger Lewis acid than Al2Cl6. In this report, Al(2)Br(6)is grafted on commercial mesoporous silica (CMS), SBA-15 and silica gel to create a solid catalyst similar to the silica-supported Al(2)Cl(6)superacid. These supported Al(2)Br(6)catalysts were characterized by NH3-Temperature Programmed Desorption (TPD), pyridine Diffuse Reflectance for Infrared Fourier Transform Spectroscopy (DRIFTS) and Magic Angle Spinning Nuclear Magnetic Resonance …

Solvation Structures And Dynamics Of Small Molecules: Experimental And Computational Studies Using Carbonyl Vibrational Modes As Probe, Xiaoliu Zhang

LSU Doctoral Dissertations

Solutions are ubiquitous in both the global environment and the human body, and play a significant role in scientific research and industrial production. The structures and dynamics of solutions have been studied for centuries. However, conventional experimental methods, whose intrinsic measuring time is on the order of nanoseconds to microseconds, could not detect the fast dynamics taking place in the solution on the timescale of femto- and pico-second. In this dissertation, the ultrafast two-dimensional infrared (2DIR) spectroscopy was applied to characterize the structure and dynamics in three different types of solutions on the sub-picosecond timescale. Linear Fourier transform infrared spectroscopy …

Phosphorus Variability In The Area Of Influence Of The Mid-Barataria Sediment Diversion, Peter Mates

LSU Master's Theses

Man-made levees along the lower Mississippi River prevent delivery of sediment from building and maintaining Louisiana’s coastal wetlands. The Mid-Barataria sediment diversions is designed to reintroduce Mississippi River water, sediment, and nutrients into the sediment-starved Barataria Basin. Phosphorus (P) is an important macronutrient for regulating primary production in coastal marine ecosystems. Wetlands can serve as a sink or source for phosphorus to the overlying water column through various retention and release processes, dependent on concentration. Louisiana coastal systems can be phosphorus limited due to much higher concentrations of bioavailable Nitrogen in river water. The high soluble molar N:P ( >50:1) …

Antimicrobial Strategies For Topical Applications, Kelsey Marie Lopez

LSU Doctoral Dissertations

Bacteria can thrive in diverse environments and are often harmless or beneficial. Bacteria in digestive tracts is one example of beneficial bacteria; however, bacteria can be harmful and when this type proliferates, it can cause infections within hosts. Bacterial infections are easily treated with antibiotics in most cases. However, bacteria are also capable of developing mutations which could cause them to become multi-drug resistant and eventually, “superbugs.” Therefore, the development of novel antimicrobial agents and materials capable of combating drug-resistant bacteria is necessary. Research presented in this dissertation focuses on different strategies for minimizing and preventing topical bacterial infections using …

Seasonal Transport Of Dissolved Inorganic Carbon And Total Alkalinity Across The Louisiana Shelf, Michelle M. Anderson

LSU Master's Theses

Rivers and wetlands are a major source of terrestrial derived carbon for coastal ocean margins. Unfortunately, Louisiana’s wetlands are threatened by ongoing high rates of erosion, deterioration, and unprecedented rates of river water discharge that changes seasonally, leading to a net loss of terrestrial carbon into the northern Gulf of Mexico (nGOM). There exists a current lack of understanding about the distribution of dissolved inorganic carbon (DIC) and total alkalinity (TAlk) within the shallowest regions of the Louisiana shelf. Even less is known about how the transport of DIC alters seasonally with changes in river outflow and shelf currents. Quantifying …

Design, Synthesis And Characterization Of New Superconductors, Xin Gui

LSU Doctoral Dissertations

Design and synthesis of new materials are a long-standing goal for chemistry, physics and material science, especially those with intriguing properties such as magnetism and superconductivity. With consideration and incorporation of the highlights in some existing design rules, we successfully designed and discovered the superconductivity in BaPt₂Bi₂, SrSnP and Yb_xPt₅P.

With the help of valence electron counting method, we synthesized a new intermetallic compound, BaIr₂Ge₂, which was then found to be non-superconducting above 1.8 K. Thus, we considered both valence electron counting and chemical pressure adjustment to reach …

Copper And Ruthenium Pyridyltriazole Complexes And Their Reactivity Toward Carbon Dioxide And Water, Fatemeh Khamespanah

LSU Doctoral Dissertations

A variety of pyridyltriazole ligands are readily available via click type cycloaddition of alkynylpyridines and azides. We made functionalized tetradentate m-xylylenebis(pyridyltriazole) (m-xpt) ligands with NH₂ and NMe₂ electron-donating and NO₂ electron-withdrawing substituents on the pyridine moieties. Complexation of these ligands with Cu(II) gives dimeric macrocycles with square pyramidal geometry at Cu centers. Previous work in our lab with the unsubstituted [Cu₂(m-xpt)₂(NO₃)₂]²⁺ complex showed reduction to Cu(I) by using ascorbate as reducing agent. Oxidation of the Cu(I) solution in air results in formation of …

Investigating Geochemical Processes Of Fluid-Rock Interactions On Materials Related To Energy And Environment, Zelong Zhang

LSU Doctoral Dissertations

Understanding the potential processes of radionuclides released from nuclear waste forms is essential to the safe disposal and containment of nuclear waste. Iodoapatite, a potential waste form for radioiodine, was chosen as a model system to examine the impact by common aqueous anions on iodine release processes. Four semi-dynamic leaching tests were performed using 0.1 mol/L NaCl, Na₂CO₃, Na₃PO₄, and Na₂SO₄ solutions respectively under 90 °C, 1 bar, fixed S/V ratio 5/m (sample surface area to solution volume), and with 24-hour replacement of the leaching solutions. Solution analysis and …

Pyrene Pyrimidine Derivatives: Synthesis, Characterization And Applications, John Kihara Mathaga

LSU Master's Theses

In this thesis, development of new materials to the field of optoelectronics were studied. Optoelectronic devices based on organic semiconductors in order to replace their inorganic counterparts have been an increasing focus of research in recent decades. Organic light-emitting diodes (OLEDs) have gained commercial acceptance for their potential use in high-resolution displays and solid-state lighting. This general acceptance is despite the fact that organic electronic concepts (solar cells, transistors and detectors) are still in an early stage of development. OLEDs materials intrinsic advantages, like low power consumption as compared to LED counterparts, a tunable color range, ease of manufacturing, and …

Synthesis, Characterization, And Investigation Of Metal Ion Quenching In Fluorescent Carbon Dot Surrogates For Particulate Matter Black Carbon And Evaluation Of Cellular Health Effects Due To The Surrogate Materials, Christopher Lee Sumner Jr

LSU Doctoral Dissertations

Black carbon (BC) is an environmental pollutant of particular concern to many international organizations for both its health effects and environmental effects. Probing health effects of BC as produced in the environment is difficult due to the complex nature of environmental pollutants found in their naturally occurring state. Fluorescent carbon dots (FCDs) were chosen to be used as a surrogate for BC. In the process of examining FCDs and their behavior as surrogates, information was gained on the health effects and behavior of FCDs as a class of nanomaterials for cell and tissue studies, which is outlined in this dissertation. …

New Synthetic Transformations Utilizing Silyloxyallyl Cations And Epoxonium Ions As Reactive Intermediates, Alexander Houston Cleveland

LSU Doctoral Dissertations

The development of new chemical transformations is of paramount importance in organic chemistry. In fact the study and creation of new reactions often uncovers new chemical reactivities and creates a new area of chemistry. The purpose of this dissertation is to present the development of new synthetic reactions that were uncovered through previous discoveries. Additionally the underlying theme of this work relies on the intermediacy of cationic reactive intermediates such as silyloxyallyl cations and epoxonium ions. Chapters 1 and 2 present the reactivity of novel silyloxyallyl cations. These cationic species are generated via the mild ionization of a-hydroxy silylenol ethers …

Behavior Of Iron Species And Free Radicals In Ambient Pm2.5 And Pm Surrogates, Cholena Russo Ren

LSU Doctoral Dissertations

Air pollution, consisting of ambient particulate matter (PM), has been a rising health concern to the public. PM contains free radicals and have been known to damage human cells; however, their free radical chemistry is not well understood. This study utilized various vacuum and/or heat treatments to study free radical behavior in PM_2.5 (particulate matter with an aerodynamic diameter of 2.5 mm or less) and PM surrogates and simulated sunlight effects on PM_2.5. To mimic PM, iron-silica catalysts (i.e. PM surrogates) were synthesized and real-world ambient PM_2.5 was selected. The free radicals in PM_{2.5 …}

3d-Printed Structured-Illumination Neutron Optics For Phase Contrast Imaging With A Triga Neutron Source, Bridget Cadigan

Honors Capstones

No abstract provided.

Dissipation Of Benzobicyclon And Benzobicyclon Hydrolysate In A Louisiana Rice Field, Xavier Poole

LSU Master's Theses

Pesticide resistance in rice fields is an ongoing issue that has resulted in the development and use of pesticides with new modes of action. Benzobicyclon is the first registered hydroxyphenylpyruvate(HPPD)-inhibiting pesticide in the United States and has gained attention as a resistance management strategy to control weed pests in rice fields. Understanding the environmental fate and dissipation mechanisms of benzobicyclon is important due to the unique rotation of rice and crayfish in Louisiana on the same fields. Benzobicyclon persistence into the crayfish growing seasons may lead to unintended consequences for crayfish growth and production, assuming there is toxicity to crawfish. …

Assessment Of Soil Protein And Refractory Soil Organic Matter Across Two Chronosequences Of Newly Developing Marshes In Coastal Louisiana, Usa, Stuart Alexander Mcclellan

LSU Doctoral Dissertations

The impacts of sea-level rise and hydrologic manipulation are threatening the stability of coastal marshes throughout the world, thereby increasing the potential for re-mineralization of soil organic matter (SOM) in these systems. Such threats have prompted marsh restoration efforts, particularly in coastal Louisiana, yet it is unclear how the slowly decomposing (refractory) and quickly decomposing (labile) fractions of SOM may be differentially affected by different approaches to marsh restoration. Additionally, otherwise labile compounds may accumulate in the soil via a range of protective mechanisms, including rapid burial and association with organic compounds that are thought to enhance soil aggregation, such …

Influencing Factors On The Velocity And Temperature Of Propagating Fronts In Acrylate Composites, Samuel Morris Bynum

LSU Doctoral Dissertations

Thermal frontal polymerization is a type of polymerization in which a localized reaction zone propagates through an unstirred system. It is incumbent upon the production and transport of heat produced as a result of the exothermic reaction associated with free-radical polymerization. First discovered in the 1970s, frontal polymerization has been since utilized to produce a variety of different materials, utilizing a variety of different chemistries. The temperature of the propagating front and the velocity at which it propagates can be influenced via chemical or physical means. We show that through careful selection of monomers and control of the concentration of …

Modeling And Simulations Of Peptoids, Pu Du

LSU Doctoral Dissertations

Polypeptoids, or poly-N-substituted glycines, are a class of sequence defined polymers that are structural mimics of polypeptides. Polypeptoids currently have received a growing interest due to their improved thermal stability, larger chemical diversity, and easier synthetic pathways as compared to peptides. Their lack of backbone hydrogen bonding and stereochemistry coupled with their easily tunability make them an ideal prototypical model system to study the effect of secondary/non-covalent interactions on self-assembly in solution. In order to develop a molecular level understanding of the effect of secondary interactions on polypeptoid self-assembly, systematic studies were carried out using molecular dynamics simulations on several …

Simultaneous Enhancement Of Near-Infrared Emission And Dye Photodegradation In A Racemic Aspartic Acid Compound Via Metal-Ion Modification, Frank R. Fronczek, Jian Xu

Faculty Publications

Changing functionalities of materials using simple methods is an active area of research, as it is "green" and lowers the developing cost of new products for the enterprises. A new small molecule racemic N,N-dimethyl aspartic acid has been prepared. Its structure is determined by single-crystal X-ray diffraction. It is characterized by FTIR, XPS, 1 H NMR, and mass spectroscopy. Its near-infrared luminescence can be enhanced by the combination of metal ions, including Dy3+, Gd3+, Nd3+, Er3+, Sr3+, Y3+, Zn2+, Zr4+, Ho3+, Yb3+, La3+, Pr6+/Pr3+, and Sm3+ ions. An optical chemistry mechanism upon interaction between the sensitizer and activator is proposed. …

Hierarchical Conjugated Polymer Systems Prepared By Controlled Chain-Growth Polymerization, Chunwa Peter Kei

LSU Doctoral Dissertations

π-Conjugated polymer materials may have a significant economic impact on society by providing means for designing affordable, flexible, and portable organic electronic devices. Their successful commercialization will depend on major scientific advancements, which will challenge human society to seek out ever more detailed and fundamental processes to command. Controlled polymerization affords such a power; allowing for the design of meticulous and precisely defined systems granting detailed insight into structure-property relationships in the polymer materials and bettering understanding of novel physical phenomena.

This dissertation primarily focuses on development and preparation of well-defined hierarchically organized macromolecular systems. The novel chain-growth polymerization methodologies …

The Effects Of Temperature On The Yields Of Aliphatic And Aromatic Products From The Supercritical Pyrolysis Of 1-Octene, Elizabeth Anne Hurst

LSU Doctoral Dissertations

Prior to their combustion, fuels for future high-speed aircraft are expected to experience supercritical conditions, leading to the production of polycyclic aromatic hydrocarbons (PAH), precursors to solid carbonaceous deposits, via pyrolytic reactions. These solid deposits can clog fuel-transfer lines, causing unsafe aircraft operation. To prevent the formation of fuel-line deposits, it is critical to understand the reaction pathways that lead to PAH formation in the supercritical fuel pyrolysis environment.

To better understand the role of large 1-alkenes in PAH formation, supercritical pyrolysis experiments with model fuel 1-octene, a representative 1-alkene product from supercritical n-alkane pyrolysis, have been performed. The …

Electrification Ionization: Fundamentals And Applications, Bijay Kumar Banstola

LSU Doctoral Dissertations

Electrification ionization is a method to produce ions from solid samples by charge separation. This separation of charge can be enhanced by organic molecules known as matrix compounds to produce highly charged molecules. In this research, new methods were developed for the application of electrification ionization for surface analysis and the ionization mechanism was investigated. First, an electrification ionization matrix was used for tissue imaging using laser ablation. A two-component matrix of 2-nitrophloroglucinol and silica nanoparticles was found to increase the number of multiply charged ions from the tissue. Images of mouse brain with multiply charged ions were obtained. In …

Detection Of Chalk In Single Kernels Of Long-Grain Milled Rice Using Imaging And Visible/Near-Infrared Instruments, Christopher K. Addison

Faculty Publications

Background and objectives To maintain the competitiveness of U.S. long-grain rice in U.S. and foreign markets, having translucent whole milled grain is critical. An objective technique to detect grain chalk, opaque areas in the grain, will provide breeders and industry with an effective tool for developing low-chalk varieties or agronomic practices that reduce chalk occurrence. Two instruments developed at the Center for Grain and Animal Health Research, U.S. Department of Agriculture-Agricultural Research Service (USDA-ARS), a single-kernel near-infrared (SKNIR) tube instrument and a silicon-based light-emitting diode (SiLED) high-speed sorter, were compared with two commercially available imaging instruments, WinSEEDLE and SeedCount used …

Emergent Functional Behaviour Of Humic Substances Perceived As Complex Labile Aggregates Of Small Organic Molecules And Oligomers, Robert L. Cook

Faculty Publications

The structural organisation of humic substances (HS) has been a central question of earth sciences for several decades. The latest experimental results have led to the recognition of HS as complex mixtures of small molecules and oligomers. We investigate the correlation between the chemical composition of HS, perceived as labile aggregates, and the emergent functions. Computational modelling was used to help to understand the processes and mechanisms on the molecular scale that occur in different fractions of the HS, fulvic acids (FA) and humic acids (HA), as they interact with metal ions and organic pollutants. The importance of non-covalent interactions …

Quartz Crystal Microbalance Based Sensors For Detection And Discrimination Of Volatile Organic Compounds Using Ionic Materials, Stephanie R. Vaughan

LSU Doctoral Dissertations

Volatile organic compounds (VOCs) are prevalent in everyday life, ranging from household chemicals, naturally occurring scents from common plants and animals, to industrial-scale chemicals. Many of these VOCs are known to cause adverse health and environmental effects and require regulation to prevent pollution. Detecting VOCs plays a critical role in food quality control, environmental quality control, medical diagnostics, and explosives detection. Thus, development of adequate sensing devices for detection and discrimination of VOCs is of great importance. In recent years, use of quartz crystal microbalance (QCM) based sensor arrays for analyses of VOCs has attracted significant interest. Detection of VOCs …

Development Of A Tunable Platform For The Study Of Geomacromolecular Matrices Using Controlled Radical Polymerization, Arjun Pandey

LSU Doctoral Dissertations

Soil is an important environmental component, and the study of soil processes have many practical implications such as improvement in agriculture, mitigation of climate change etc. The widespread use of Agricultural Chemicals (ACs) in modern agriculture has resulted in adverse effects in environment and human health mostly through contamination into food and water sources. Study of fate, bioavailability, and transport of ACs involves molecular level understanding of their interactions with soil. This can be challenging due to complex and heterogeneous nature of soil. One common approach used is the correlation of macroscopic properties of soil, (e.g. sorption) with empirical parameters …

Thioenamide Synthesis Inspired By Peptide Macrocycles, Joshua Allen Lutz

LSU Doctoral Dissertations

Despite advances in medicine, antibiotic resistance threatens to return once preventable diseases to the human population. The microbisporicins are 24-amino acid antibiotic peptides belonging to the lantibiotic class, which pathogens have been slow to develop resistance. The uncommon post-translational modification S-[(Z)-2-aminovinyl]-D-cysteine (AviCys) is likely crucial to their activity, and appears in a small number of other peptides with compelling biological activities. Total synthesis of an AviCys-containing peptide has eluded the chemical community.

The primary challenge of AviCys synthesis is the construction of a thioenamide functional group. We demonstrate that acid-promoted reactions between an amide and …

Ultrafast And Real-Time Dynamics Of Nanomaterials Studied By Advanced Spectroscopic Techniques, Jeewan Chaminda Ranasinghe

LSU Doctoral Dissertations

Ultrafast and nonlinear spectroscopies are used to study excited-state dynamics and monitor real-time growth dynamics of different types of nanomaterials. In the first study, the growth dynamics of colloidal gold-silver core-shell nanoparticles are studied using in situ second harmonic generation and extinction spectroscopy. The growth lifetimes are studied under different reaction conditions, resulting in different silver shell thicknesses, with spectral comparisons to finite-difference time-domain calculations. The results are consistent with a three-step growth process. During the first step of the nanoparticle growth reaction, rough and uneven surfaces are formed rapidly giving rise to plasmonic hot spots with corresponding broad, red-shifted …

Pyrenylpyridines: Sky-Blue Emitters For Organic Light-Emitting Diodes, Thenahandi Prasanthi Deepthika De Silva, Sang Gill Youm, Isiah M. Warner

Faculty Publications

A novel sky-blue-emitting tripyrenylpyridine derivative, 2,4,6-tri(1-pyrenyl)-pyridine (2,4,6-TPP), has been synthesized using a Suzuki coupling reaction and compared with three previously reported isomeric dipyrenylpyridine (DPP) analogues (2,4-di(1 pyrenyl)pyridine (2,4-DPP), 2,6-di(1-pyrenyl)pyridine (2,6-DPP), and 3,5-di(1-pyrenyl)-pyridine (3,5-DPP)). 0 revealed by single-crystal X-ray analysis and computational simulations, all compounds possess highly twisted conformations in the solid state with interpyrene torsional angles of 42.3 degrees-57.2 degrees. These solid-state conformations and packing variations of pyrenylpyridines could be correlated to observed variations in physical characteristics such as photo/thermal stability and spectral properties, but showed only marginal influence on electrochemical properties. The novel derivative, 2,4,6-TPP, exhibited the lowest degree …

Turn-On Near-Infrared Fluorescent Sensors For Selective Monitoring Of Kinase Activity, Gerard Thomas Ducharme

LSU Doctoral Dissertations

Reliable and selective detection of specific biopolymers is critical in a broad range of biomedical and technological areas, including availability of simple and efficient point-of-care-compatible systems for the detection of prognostic, pharmacodynamic and predictive biomarkers. Monitoring epidermal growth factor receptor (EGFR) tyrosine kinase is of major significance due to its link to many epithelial cancers. This task is complicated by the high rate of mutation occurring in patients treated with kinase inhibitors. This dissertation describes a conceptually novel design and synthesis of turn-on near-infrared fluorescent sensors for selective and sensitive detection of EGFR. The fluorescent signal generation mechanism is based …

Sequence-Defined Ionic Peptoid Block Copolymers: Synthesis And Solution Self-Assembly, Garrett Leigh Sternhagen

LSU Doctoral Dissertations

This work covers efforts to develop a peptoid-based model system for systematically studying the role of ionic functional groups in determining the structure of ionic block copolymer (BCP) self-assemblies in water. A key challenge in the study of polyelectrolytes is the lack of synthetic control over the location of ionic monomers along a polymer chain. We developed a model system based on sequence-defined ionic peptoid BCPs having discrete chain length and precisely positioned ionic monomers along the chain to specifically address this issue. In Chapter 1, synthetic strategies to access well-defined polypeptoids and their application in BCP synthesis are reviewed. …