Chemistry Commons^™

From The River To The Gulf: An Investigation Of Biogeochemical Cycling In Wetland Soils And Coastal Shelf Sediments, Katie Bowes

LSU Master's Theses

Louisiana is home to 40% of the coastal wetlands in the lower 48 states, yet accounts for 80% of the coastal wetland loss in this region. This loss is attributed to decreased sediment supply, levee alteration, sea level rise, channelization, and subsidence. The levee system in Louisiana disconnected coastal wetlands from the main stem of the Mississippi River (MSR), reducing the amount of land-building sediment that reaches coastal wetlands. This disconnection also allows a greater percentage of river discharge, including agricultural contaminants and runoff, to flow into the northern Gulf of Mexico (NGOM).

The 2012 Coastal Master Plan proposed eight …

Calculation Guided Rational Design And Synthesis Of Novel Cationic Fluorescent Meso–Pyridinium Bodipys For Bio-Imaging, Daniel J. Lamaster

LSU Doctoral Dissertations

Chapter 1 contains a brief overview of the history, synthesis, and properties of BODIPY dyes as well as that of the biomedical applications of bio-imaging and photodynamic therapy. Additionally, an overview of the theoretical framework of density functional theory and its time-dependent variant are provided. In Chapter 2, the effects of structural modification on the electronic structure and electron dynamics of cationic meso-(4-pyridyl)-BODIPYs were investigated. A library of 2,6-difunctionalized meso-(4-pyridyl)-BODIPYs bearing various electron-withdrawing substituents was designed and DFT calculations were used to model the redox properties, while TDDFT was used to determine the effects of functionalization on the excited …

Influence Of Salinity, Sunlight, And Sediment On The Toxicity Of Pesticides In Three Non-Target Organisms, Emily Noelle Vebrosky

LSU Doctoral Dissertations

Pesticides used in the United States must undergo registration by the United States Environmental Protection Agency (USEPA), after a multitude of analyses ranging from environmental fate to aquatic toxicological impacts to human risk exposure. Testing varies for each chemical, some requiring more testing than others. In many cases, environmental factors are restricted in the analysis of chemical behavior and organismal testing is limited to larvae. Many pesticides are formulated to breakdown in the environment by means of photolysis, hydrolysis, or oxidation, either to ensure low-persistence, limited transport, or to form the active ingredient (pro-pesticides). Environmental influences on chemical behaviors include …

High-Dimensional Isotope Relationships, Yuyang He

LSU Doctoral Dissertations

High-dimensional isotope relationships describes the relationships of two or more element or position-specific (PS) elements in the same molecule or ion. It provides us more powerful tools to study reaction mechanisms and dynamics. Chapter 1 is about dual or multiple stable isotope relationship on δ-δ (or δ'-δ') space. While temporal data sampled from a closed-system can be treated by a Rayleigh Distillation Model (RDM), spatial data should be treated by a Reaction-Transport Model (RTM). Here we compare the results of a closed-system RDM to a RTM for systems with diffusional mass transfer by simulating the trajectories on nitrate's δ'^{18 …}

Ultrafast And Nonlinear Spectroscopy Of Nanomaterials, Rami Anthony Khoury

LSU Doctoral Dissertations

Ultrafast and nonlinear spectroscopies are implemented in the investigation of excited-state dynamics and structural properties of materials and nanomaterials. In the first study, the excited-state dynamics of size-dependent colloidal TiO₂-Au nanocomposites are investigated using ultrafast transient absorption spectroscopy. The dynamics corresponding to the plasmon depletion band are characterized by electron-phonon and phonon-phonon coupling lifetimes that are observed to be independent of the gold nanocluster shell thickness. The excited-state dynamics corresponding to the interband transition of gold is also spectrally overlapped with the interfacial electron transfer lifetime, which is shown to decrease as the nanocluster shell thickness increases. In …

Nmr Structural Investigation Of Chlamydial Protein Complex And Lysine Glycomimetic For Drug Design, Abigael Chebichiy Songok

LSU Doctoral Dissertations

Research and design of drugs for treatment against microbial infections require the study of pathogenic proteins involved during infection and replication. Drugs can be designed to interfere with the interaction network of these pathogenic proteins and inhibit the infection process. Determination of the structure and ligands of the target proteins in microbes is essential for designing mechanistic-based drugs. Two Chlamydia proteins involved in host cell invasion were investigated in this study. The goal is to identify amino acids involved at the binding interface of Chlamydia chaperon proteins Scc1 and Scc4 by solution NMR spectroscopy. This information will give a lead …

New Platinum(Ii) And Rhenium(I) Complexes Of "Linear" Chelate Ligands Terminated With Pyridyl Or Imidazolyl N-Donor Groups, Himali Kokila Ranasinghe Pilana Vithanage

LSU Doctoral Dissertations

The overall goal of this dissertation research is to design, synthesize, and study new Pt(II) and Re(I) complexes relevant to biomedical applications. One of the projects involves the assessment of the interactions of bulky tridentate carrier ligands with a bound guanine nucleobase derivative (G) in platinum complexes, with a goal of developing chemistry potentially relevant to active anti-cancer Pt drugs. In another project, the fac-[Re^I(CO)₃]⁺ core is used to prepare novel Re(I) complexes with the purpose of developing new linking chemistry relevant to ^99mTc and ¹⁸⁷Re radiopharmaceuticals. This research explores …

Free-Radical Polymerization Of Acid-Containing Deep Eutectic Solvents, Kylee Fazende

LSU Doctoral Dissertations

The forefront of this study explored polymerization, specifically thermally-initiated, free-radical frontal polymerization of (meth)acrylic acid monomers while the monomers acted as a hydrogen bond donor of a deep eutectic solvent. These frontal polymerizations were shown to exhibit unusual front velocities and, in some cases, lower front temperatures than the frontal polymerization of the neat monomers or systems containing inert analogs in the place of the hydrogen bond acceptor of these monomer-containing deep eutectic solvents. The frontal polymerization will occur with a range of initiator concentrations including ones that were too low for the pure monomer systems to sustain a front. …

Accelerated Broadband Spectra And Attosecond Charge Migration Simulations Using Real-Time Time-Dependent Density Functional Theory, Adam S. Bruner

LSU Doctoral Dissertations

In this dissertation, the calculations of light-matter interactions offer insight into the structure and dynamical response of electrons in molecular systems. Such information is useful for characterizing molecules, electronic structure, photochemistry, photomaterials, and a host of other applications. In the first part of this work, simulations of broadband absorption spectra are accelerated by the use of Pad´e approximanants of Fourier Transforms and dipole decomposition. Electronic absorption spectra from valence and core levels are obtained using time-dependent methods and compared to results from established perturbative techniques. In addition, core level absorption spectra are calculated for a nickel porphyrin and shown to …

Visualization And Quantification Of Cancer-Associated Enzymes With Fluorescent Small-Molecule Substrate Probes, Zhenhua Shen

LSU Doctoral Dissertations

Fluorescence imaging can be used both as a tool to diagnose diseases and guide treatment in clinical settings, and as a technique to monitor dynamic events or biological species in basic research. Therefore, there is a great need for the development of a multitude of fluorescent probes that can be incorporated with fluorescence imaging techniques to track and report endogenous enzymes with high specificity and selectivity. In contrast to always-on and targeted always-on fluorescent probes that continually emit light, activity-based substrate probes either emit low numbers of photons or are completely quenched. They can be converted to highly fluorescent reporters …

Investigation Of Structure And Dynamics Of Deep Eutectic Solvent Using Infrared Spectroscopy, Yaowen Cui

LSU Doctoral Dissertations

Deep Eutectic Solvents (DES) are liquid mixtures prepared from solids. As a new class of green solvents, DES not only share many properties with ionic liquids, such as low volatility, conductivity, tailorable constituents, but also have some advantages over ionic liquids, like easier preparation, safe and inexpensive materials, biodegradability, low toxicity, and excellent solubility. Because of those attractive properties, DES has been studied in many scientific and engineering fields. However, compared with the great number of studies of the application, many questions about structure and dynamics of DES are unanswered. To shed light on the mystery of solvent or solvation …

Workflows For X-Ray And Neutron Interferometry/Tomography As Applied To Additive Manufacturing, Jumao Yuan

LSU Doctoral Dissertations

Grating-based interferometry/tomography is being rapidly developed for non-destructive evaluation of additive manufacturing test articles. An application requiring an efficient workflow is extremely necessary for stress and fatigue testing samples.

At present, scientific workflows play an important role for computational experiments in additive manufacturing 3D printing and interferometry/tomography imaging analysis. A clear workflow template allows scientists to process experiments easier and faster. Work flow library grows, but to find an appropriate workflow for their task is challenging. In our research, there are mainly three portions in the workflow, interferometry analysis, image reconstruction and 3D visualization. Currently, the hierarchy of workflows in …

Effects Of Enhanced Efficiency Nitrogen Fertilizers On Agronomic Parameters And Loss Pathways In The Subtropical Mississippi Delta Region, Scott Michael Pensky

LSU Master's Theses

Minimizing nitrogen (N) loss is critical for improving N use efficiency (NUE) in crop production and reducing its effects on the environment. Management practices such as seasonal application timing of N fertilizers and the addition of enhanced efficiency N fertilizers (EENFs) were investigated for the high N requirement of the two most common cereal crops globally, corn (Zea mays L.) and wheat (Triticum aestivum L.), in the subtropical climate of Louisiana. Field research was established during the 2016 and 2017 seasons at the LSU Agricultural Center’s Dean Lee and Central research stations to examine the effect of different EENFs and …

Evaluation Of Controlled-Release Nitrogen And Potassium Fertilizer In Louisiana Sugarcane Production, Samuel Kwakye

LSU Master's Theses

Sugarcane (Saccharum spp) production is an integral part of Louisiana's economy. Proper fertilizer management, particularly nitrogen (N) and potassium (K), optimizes sugarcane production. An experiment was established in 2015 at the LSU AgCenter Sugar Research Station in St. Gabriel, Louisiana to: (1) assess the effect of N and K fertilizer sources on sugarcane yield and quality parameters, and (2) monitor the changes in inorganic N and K levels in the soil at different sugarcane growth stages. The experiment was arranged in a randomized complete block design on a Sharkey clay soil and complete randomized design on a Commerce …

Modifications To Para-Menthane-(3,8)-Diol To Increase Mosquito Repellency, Heidi Nowakowski

Honors Capstones

No abstract provided.

Higher Energy Gap Control Of Fluorescence In Conjugated Polymers, Chien-Hung Chiang

LSU Doctoral Dissertations

Chemo- and biosensors based on fluorescent conjugated polymer benefit from greater detection sensitivity due to amplification of the electronic perturbations produced by analyte binding. This amplification stems from the exciton-transporting properties of conjugated polymers. A conventional design paradigm relies on the analyte binding events which generate sites of lower energy relative to the polymer energy: either fluorescence quenching sites (turn-off sensors) or bathochromically shifted fluorophores (turn-on sensors). In both type sensors, the excitons migrate to the lower-energy site created by analyte binding.

This dissertation primarily focused the investigation of an alternative paradigm when analyte binding creates higher energy gap sites …

Synthesis, Characterization, And Assessment Of Cationic Polypeptoids Toward Gene Delivery And Development Of Air Stable N-Substituted N-Thiocarboxyanhydrides, Jessica Michelle Simpson

LSU Doctoral Dissertations

Peptoids are a class of peptidomimetic polymers, which have attracted much attention over the years. Due to their structural similarity to peptides, this group of polymers affords good biocompatibility making them of interest for biomedical applications. This dissertation is largely about the design, synthesis, and characterization of cationic polypeptoids for biological applications, particularly nonviral gene delivery. The dissertation will also cover the development, characterization, and polymerization behavior of a new, air stable N-thiocarboxyanhydride (NTA) monomer.

Introducing functionality, such as small biomolecules and organic compounds can provide distinctive properties to the polymers. Chapter 1 introduces gene therapy and concepts pertinent …

Synthesis And Characterization Of Covalent Adaptable Networks Comprised Of Dynamic Imine And Aminal Covalent Bonds, Albert Chao

LSU Doctoral Dissertations

The dissertation is about the design, synthesis and characterization of materials comprised of covalent adaptable networks (CANs). There are three chapters within this dissertation.

Chapter 1 contains a short overview of conventional thermosets and thermoplastics. A new strategy of combining advantages from thermosets and thermoplastics is utilizing dynamic covalent chemistry (DCC) for material design. Dynamic covalent bonds are able to undergo dynamic exchange which allow the material to adapt to a new state when under stimuli such as stress or strain. Material comprised of such reversible networks is called covalent adaptable networks (CANs). These types of reversible covalent bonds followed …

Legacy Contaminants In The Northern Gulf Of Mexico Shelf, Jessica N. Landry

LSU Master's Theses

The Mississippi River watershed is the third largest in the world and drains from 31 states in the United States. Due to its route through the U.S., it passes through hundreds of EPA labeled Superfund sites as well as agricultural and suburban watersheds. These sites are known to have historical chemical contamination, and as a result chemicals can be transported by runoff down the Mississippi River into the Gulf of Mexico where their ultimate fate is unknown. Organochlorine chemicals are known to be persistent and are found in agricultural land as well as US EPA Superfund sites, especially DDT, PCBs, …

Chemotherapeutic Applications Of Rhodamine Based Nanogumbos, Nimisha Bhattarai

LSU Doctoral Dissertations

The work presented in this dissertation employs nanomaterials derived from a group of uniform materials based on organic salts (GUMBOS) for selective chemotherapeutic applications. GUMBOS, similar to ionic liquids, are organic salts consisting of a bulky cationic and anionic moiety. In contrast to ionic liquids, these materials have melting points ranging from 25–250 °C, making them solid phase at room temperature. Similar to ionic liquids, GUMBOS display tunable properties, such as hydrophobicity and solubility, through counter ion variation. These tunable properties provide a variety of applications for these GUMBOS, including selective chemotherapeutics applications. The …

Innovative Monte Carlo Methods For Sampling Molecular Conformations, Aliasghar Sepehri

LSU Doctoral Dissertations

Sampling molecular conformations is an important step in evaluating physical, mechanical, hydrodynamic, and optical properties of flexible molecules especially polymers. One powerful method for this purpose is configurational-bias Monte Carlo in which one random segment of a molecule is chosen, all segments toward one random end are removed, and then regrown segment by segment to produce a new geometry to be accepted/rejected according to probability laws. The advantage of this method is the ability to generate acceptable conformations that are favorable for intra- and intermolecular energies to save computational costs. However, when there are several interdependent energetic terms, trial generation …

Biomedical Applications Of Hydrogels And Gumbos, Kelsey Elizabeth Mcneel

LSU Doctoral Dissertations

Sodium deoxycholate (NaDC) is a small bile salt that was used in this dissertation to produce gelation of tris(hydroxymethyl)amino-methane (TRIS) solutions above, below, and near the pKa of NaDC. These solutions respectively yielded a neutral gelator, a charged gelator, and a mixture of each. Impacts of ionic interactions on gel formation were studied in detail and showed that pH can be used to modify many hydrogel properties including sol-gel temperature, crystallinity, and mechanical strength. It was also observed that pH modification of the hydrogels affected nanoparticle formation. Nanoparticles derived from a Group of Uniform Materials Based on Organic Salts (nanoGUMBOS), …

Analysis Of Veterinary Drug Residues In Imported And Domestic Crawfish Using Liquid Chromatography—Mass Spectrometry, Emily Kate Wall

LSU Master's Theses

Aquaculture production has greatly increased over the past few decades, and will continue to grow as the world fisheries become overfished and demand for seafood increases. With increased production comes more intense cultivation methods and heavy use of formulated feeds that may contain veterinary drug residues. Currently no antibiotics are allowed in the U.S. for crawfish aquaculture; yet, detectable levels of various antibiotics have been found in imported seafood samples.The FDA is responsible for testing aquaculture products entering the United States, but only has the capabilities to test a minimal amount of those imports. Additionally, for crawfish there is only …

Expression, Purification And Characterization Of Egf27 From The Notch1 Abruptex Region, Huimin Zhong

LSU Master's Theses

Notch proteins are transmembrane proteins and act as receptors in Notch signaling, which is related to diverse developmental diseases including cancer.^1-2 The mouse Notch1 protein contains 36 tandem epidermal growth factor-like (EGF) repeats in the extracellular domain (ECD).^1-2 Our research project focused on the structural study of the Abruptex region consisting of EGF24-29 in the ECD. The fact that this region is a potential competitor to a Notch ligand, because of its high glycosylation and flexibility, makes it important to solve the three-dimensional structure and investigate the glycosylation effect on the structure of the Abruptex region.³ By …

Development Of Remote Hydroxylation Via Redox Catalysis And Mild Activation Of Thioglycosides For O-Glycosylation, Kristina Deveaux

LSU Doctoral Dissertations

The focus of this dissertation is the development of a C-H functionalization method using redox catalysis and the synthesis of saccharides using thioglycosides. Chapter 1 is a review of C-H functionalization and visible-light photoredox catalysis. Over the years there have been many significant contributions to the field of C-H functionalization. Select examples have been discussed and a foundation for the method developed in chapter 2 has been outlined. Chapter 2 discusses the development and optimization of a C-H functionalization method. This approach uses the Tz^o directing group and Ir(ppy)₃ to activate a remote C-H bond via 1,6- and …

Nanopatterns Of Zinc Phthalocyanines, Gold Nanoparticles, And Porphyrins Prepared Using Particle Lithography: Characterization Of Patterning Steps With Scanning Probe Microscopy, Ashley Marie Taylor

LSU Doctoral Dissertations

The growth and self-assembly of molecules on surfaces can be directly visualized at the molecular level using studies which combine nanoscale lithography and high-resolution imaging. Nanopatterning provides a unique and practical approach for direct views of surface changes after the key chemical steps of nanopatterning, providing landmarks and baselines for measuring growth in vertical and lateral dimensions. Controlling the arrangement of materials on surfaces at the nanoscale can be achieved using particle lithography. Arrays of well-defined nanostructures can be prepared with reproducible geometries and arrangement. Results for the preparation of nanopatterns produced with particle lithography are presented using high resolution …

Coupled Plasmon/Molecule Dynamics Near Core-Shell Nanoparticles: Synthesis, Ultrafast Characterization, And Quantum/Classical Modeling, Holden Tyler Smith

LSU Doctoral Dissertations

In this dissertation, the resonance coupling of chromaphoric dyes adsorbed on the surface of plasmonic nanoparticles (NPs) are investigated using a combined theoretical and experi- mental approach. Colloidal gold, gold-silver core-shell, silver-gold core-shell, and gold-silver- gold core-shell-shell NPs are considered. These NPs are thiolated with mercaptosuccinic acid, and malachite green dyes are adsorbed to the surface of the nanoparticle (NP) via elec- trostatic interactions. Second harmonic generation is used to determine the surface to the isotherm of the molecular dyes to the colloidal nanoparticle surface. Adsorption isotherms show that the SHG intensity increases as the concentration of dye increases, reaching …

Self-Assembly Mechanisms Of Organosilanes And Porphyrins Investigated With Scanning Probe Microscopy, Phillip Charles Chambers Ii

LSU Doctoral Dissertations

This dissertation details the development of new fabrication strategies for the preparation of spatially selective surfaces by combining techniques of particle lithography and scanning probe microscopy (SPM). This combination of lithography and nanoscale surface characterization was applied to study the mechanisms of molecular level surface-assembly of organosilanes and porphyrin on surfaces of Si(111). Particle lithography was used to investigate the surface assembly of 4-chloromethylphenyltrichlorosilane (CMPS) within exposed sites of nanoholes in selected solvents and at selected temperatures to gain insight into the details of self-polymerization. Nanopillars of CMPS were generated under selected conditions of solvent and temperature and characterized with …

New Synthetic Reactions Towards Global Chlorination And Enamides Functionalization, Mirza Ardella Saputra

LSU Doctoral Dissertations

This dissertation focuses on two main projects, global chlorination and enamide functionalization, which both encompass in cationic intermediates. Inspired by the desires to find a new chlorination method, global chlorination project is emphasized in chapter one and chapter two, in which chapter one details various known chlorine-containing natural products, including alkyl chlorides and vinyl chlorides. This chapter also describes the previously known protocols to synthesize alkyl chlorides in the attempts of chlorosulfolipids total syntheses, as well as several known reactions to synthesize vinyl chlorides that are both important functional groups in organic synthesis. Chapter two depicts our novel synthetic reaction …

Hydroformylation And Aldehyde-Water Shift Catalysis By Dirhodium Tetraphosphine Complexes, Marshall Douglas Moulis

LSU Doctoral Dissertations

The use of a unique tetraphosphine ligand (et,ph-P4) allows for the chelating of two rhodium centers to perform bimetallic coopertivity in hydroformylation reactions to better the yields the linear aldehyde product. The proposed catalyst is [Rh₂(μ-H)₂(CO)₄(rac-et,ph-P4)]²⁺ and has been studied by in situ FT-IR and NMR. When tested in a polar phasic acetone/water (30 % by vol.), the catalyst forms a monocationic system [Rh₂(μ-H)₂(CO)₄(rac-et,ph-P4)]⁺ that has an initial TOF of 26 min^-1, selectivity of 27:1 L:B, and low byproducts of …