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Articles 1 - 26 of 26
Full-Text Articles in Physical Sciences and Mathematics
Hybrid Inorganic Core- Conjugated Polymer Shell Nanoparticles Prepared By Surface-Initiated Polymerization, Sourav Chatterjee
Hybrid Inorganic Core- Conjugated Polymer Shell Nanoparticles Prepared By Surface-Initiated Polymerization, Sourav Chatterjee
LSU Doctoral Dissertations
Hybrid core-shell nanoparticles have attracted attention due to their unique characteristics which combine properties of the inorganic core and organic shell in a way that generates new properties which do not exist for the two individual parts. This makes them promising candidates for the design of stimuli-responsive materials, chemo- and biosensors, and various biomedical applications. In this dissertation research, we designed and prepared a series of hybrid environmentally responsive nanoparticles where fluorescent block copolymers, including various combinations of polythiophene (PT), poly(p-phenylene) (PPP), poly(3-hexylthiophene) (P3HT) and polyallene (PA), were grafted on the surface of inorganic nanoparticles using surface-confined Kumada catalyst-transfer polymerization. …
Studies Of The Properties Of Designed Nanoparticles Using Atomic Force Microscopy, Steve Matthew Deese
Studies Of The Properties Of Designed Nanoparticles Using Atomic Force Microscopy, Steve Matthew Deese
LSU Doctoral Dissertations
The purpose of the research in this dissertation was to elucidate the intrinsic properties of how nanoparticles are different from bulk materials. This was done by mechanical and electronic studies of the properties of designed nanoparticles using advanced modes of atomic force microscopy. Information relating to the work functions, contact potential difference, Young’s Moduli, elasticity, and viscoelasticity can be investigated using state-of-the-art atomic force microscope (AFM) experiments. Subsurface imaging of polystyrene encapsulated cobalt nanoparticles was achieved for the first time using Force Modulation Microscopy (FMM) in conjunction with contact mode AFM. Previously prepared sample of polystyrene coated cobalt nanoparticles were …
Design, Synthesis And Biological Applications Of Polypeptoids And Boron Dipyrromethenes, Sunting Xuan
Design, Synthesis And Biological Applications Of Polypeptoids And Boron Dipyrromethenes, Sunting Xuan
LSU Doctoral Dissertations
The dissertation is about the design, synthesis and biological applications of polypeptoids and boron dipyrromethenes (BODIPYs). The dissertation is divided into seven chapters reporting various aspects of the background to my field of study and the results obtained during my PhD program. Chapter 1 is a concise overview of the fundamental concepts of polypeptoids and hydrogels, as well as their recent developments on synthetic strategies, property investigations, and biological applications in different fields. Chapter 2 presents the design, synthesis and potential application as tissue engineering scaffold of thermoreversible ABC polypeptoid hydrogels. A series of ABC copolypeptoids were synthesized and their …
Peptidomimetic Polymers: Advances In Monomer Design And Polymerization Methods, Brandon Andrew Chan
Peptidomimetic Polymers: Advances In Monomer Design And Polymerization Methods, Brandon Andrew Chan
LSU Doctoral Dissertations
This work is focused on the design, synthesis and characterization of polypeptide and polypeptoid polymers. The former are composed of amino acid repeat units and possess intramolecular hydrogen bonding interactions allowing for the self-assembly into well-defined secondary structures (e.g. α-helix). Polypeptoids are based on N-alkyl substituted glycine and lack intramolecular hydrogen bonding interactions, resulting in enhanced proteolytic stability and thermal processability. Physicochemical properties of polypeptoids are strongly dependent on the side chain structures, allow for control of the solubility, crystallinity, and conformation of the polymers. Well-defined polypeptides and polypeptoids are synthesized by the ring-opening polymerization (ROP) of their corresponding N-carboxyanhydride …
Thin Films Of Semiconducting Polymers And Block Copolymers By Surface-Initiated Polymerization, Sang Gil Youm
Thin Films Of Semiconducting Polymers And Block Copolymers By Surface-Initiated Polymerization, Sang Gil Youm
LSU Doctoral Dissertations
The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices, including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g. spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of pre-synthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. This dissertation mainly focuses …
Synthesis Of Functional Polypeptides And Development Of New Synthetic Strategies Toward Polypeptides, Jinbao Cao
Synthesis Of Functional Polypeptides And Development Of New Synthetic Strategies Toward Polypeptides, Jinbao Cao
LSU Doctoral Dissertations
The objective of this work is to develop a new synthetic strategy for synthesizing advanced functional polypeptides or polypeptides in general. Polypeptides are amino acids based polymers with appealing properties for different applications. One of the key challenges in polypeptide research is the synthesis of functional polypeptides under mild conditions. We developed a system based on ring-opening polymerization (ROP) of N-thiocarboxyanhydrosulfides (NTAs) to synthesize polypeptides with wide range of molecular weights under mild conditions. Owing to NTAs’ good stability, our system serves as an excellent alternative to the traditional ROP of N-carboxyanhydrides (NCA). In Chapter 1, the fundamental knowledge and …
Tip-Enhanced Laser Ablation Sample Transfer For Mass Spectrometry, Chinthaka Aravinda Seneviratne
Tip-Enhanced Laser Ablation Sample Transfer For Mass Spectrometry, Chinthaka Aravinda Seneviratne
LSU Doctoral Dissertations
In this research, atomic force microscope tip-enhanced laser ablation mass spectrometry (AFM TELA-MS), an ambient sub-micrometer scale sampling method for offline MS was developed. AFM TELA was used to transfer molecules from thin films to a suspended silver wire for off-line mass spectrometry using laser desorption ionization (LDI) and matrix-assisted laser desorption ionization (MALDI). An AFM with a 30 nm radius gold-coated silicon tip was used to image the sample and to hold the tip 15 nm from the surface for material removal using a pulsed Nd:YAG laser, which provides output at wavelengths of 532 nm in the visible, 1064 …
Design And Implementation Of Qcm Virtual Sensing Schemes For Analyses Of Volatile Organic Compounds, Nicholas Colby Speller
Design And Implementation Of Qcm Virtual Sensing Schemes For Analyses Of Volatile Organic Compounds, Nicholas Colby Speller
LSU Doctoral Dissertations
Sensor arrays have evolved as powerful approaches for providing detection and discrimination of volatile organic compounds (VOCs) as required across numerous analytical applications. Such systems typically comprise a number of cross reactive sensor elements, which generate analyte specific response patterns upon exposure to VOCs, and are known as multisensor arrays. When evaluated using statistical methods, these response patterns facilitate classification of VOCs. As an alternative, a single dynamically operated sensor could also be used to generate analyte specific response patterns. This approach is known as a virtual sensor array (VSA) and can exhibit significant advantages when compared to MSAs. Some …
Exploration Of Bimetallic Nickel And Cobalt Complexes For Catalytic Oxidative Cleavage Of Alkenes And Hydroformylation, Ciera Vonn Duronslet
Exploration Of Bimetallic Nickel And Cobalt Complexes For Catalytic Oxidative Cleavage Of Alkenes And Hydroformylation, Ciera Vonn Duronslet
LSU Doctoral Dissertations
The “old” bimetallic nickel complexes, meso- and rac-Ni2Cl4(et,ph-P4) were investigated as possible “catalysts” for the oxidative cleavage of alkenes using an unsaturated fatty acid, oleic acid, as the substrate. The “new” bimetallic nickel complexes with a stronger chelating tetraphosphine ligand, meso- and rac-Ni2Cl4(et,ph-P4-Ph), were also synthesized and tested for the oxidative cleavage of oleic acid. All four dinickel complexes were found to be active for the oxidative cleavage of oleic acid, producing extremely small amounts of aldehyde product. The Stanley research group also discovered the oxidative cleavage of alkenes using only the “old” et,ph-P4 tetraphosphine ligands with no metal centers. …
Synthesis And Characterization Of Cyclic Polypeptoids By Organo-Mediated Controlled Zwitterionic Ring-Opening Polymerization And Development Of Redox-Responsive Polypeptoid Micelles As Drug Delivery Carriers, Ang Li
LSU Doctoral Dissertations
Peptoids are peptidomimetic polymers, which have attracted much attention over the past two decades. They have similar building blocks to peptides, and the similarity makes the backbone of peptoids hydrophilic and biocompatible.1 Two types of peptoid polymers are under development. One is sequence-defined peptoids, which exhibit excellent bioactivities.2 Another one is polypeptoids. The good biocompatibility and highly tunable side chain substituents allow polypeptoids to be used broadly in future biomedical applications. Varying polymer architectures, including linear polymers, cyclic polymers, comb-like polymers, and dendrimers can provide distinctive properties to the polymers. Cyclic polymers employ a cyclic architecture and lack chain ends, …
Advanced Monte Carlo Methods For The Study Of Nucleation, Troy David Loeffler
Advanced Monte Carlo Methods For The Study Of Nucleation, Troy David Loeffler
LSU Doctoral Dissertations
The process of nucleation is an essential part of understanding and controlling phase changes in a wide array of systems. In the past theories such as Classical Nucleation Theory have been used as a tool to aid experimentalist in the study of phase mechanisms. However, recent studies have shown in detail that theories such as this are not reliable, given that it can mispredict nucleation rates by several orders of magnitude. As a result newer methodologies must be developed into order to improve upon these deficiencies. In this study we use atomistic simulations to examine the non-ideal deviations from classical …
Scanning Probe Investigations Of Multidentate Thiol And Spatially Confined Porphyrin Nanoassemblies Using Nanoscale Lithography, Xianglin Zhai Zhai
Scanning Probe Investigations Of Multidentate Thiol And Spatially Confined Porphyrin Nanoassemblies Using Nanoscale Lithography, Xianglin Zhai Zhai
LSU Doctoral Dissertations
Approaches to prepare spatially selective surfaces were developed in this dissertation for constructing nanopatterns of organic thin film materials. Nanoscale surface patterns were prepared using immersion particle lithography and scanning probe lithography combined with organothiol chemistry. Organic thin films and nanomaterials can be patterned with tunable periodicities and designed shapes by selecting the diameter of mesospheres used as surface masks or scanning probe lithography, respectively. The surface platforms of well-defined nanopatterns are ideal for high resolution investigations using scanning probe microscopy (SPM). Local measurements of surface properties and conductive properties combined with nanolithography were accomplished at the molecular level. Sample …
Synthesis And Characterization Of Polyhalogenated Boron Dipyrromethenes And Carboranylbisthiophene Oligomers, Ning Zhao
LSU Doctoral Dissertations
Chapter 1 of this dissertation shows a brief overview of fundamental concepts and classic synthetic routes of BODIPY dyes. The synthetic strategies and various application (e.g. PDT sensitizers and fluorescent indicators) of halogenated BODIPYs are also presented in this chapter. Chapters 2-4 describe the synthesis of three new polyhalogenated BODIPY platforms and their regioselective functionalization. Such new platforms provide new methodologies for producing both symmetric and asymmetric BODIPYs. Pd(0)-catalyzed cross-couplings and aromatic substitution reactions were applied to investigate the reactivity and regioselectivity of different halogen groups on the BODIPY platforms. The studies showed that the reactivity order of the halogens …
Use Of X-Ray K-Edge Tomography And Interferometry Imaging Techniques For The Studies Of Brominated Flame Retardants, Mutairu Bolaji Olatinwo
Use Of X-Ray K-Edge Tomography And Interferometry Imaging Techniques For The Studies Of Brominated Flame Retardants, Mutairu Bolaji Olatinwo
LSU Doctoral Dissertations
The work presented in this dissertation is based on the studies of flame retardancy performance of various formulations consisting of brominated flame retardants (BFRs: Saytex 8010 and Green Armor) and their synergist, antimony trioxide (Sb2O3) in high impact polystyrene (HIPS). Chemical flame retardants are incorporated in polymers to improve their flame inhibition for optimal applications in electrical and electronic devices, furniture, printers and more. These flame retardant polymer blends are studied using the Underwriters Laboratory vertical burn test (UL 94) and X-ray imaging techniques such as X-ray K-edge absorption tomography and X-ray grating interferometry. The UL 94 burn test is …
Ultrafast And Nonlinear Spectroscopy Of Colloidal Nanomaterials, Tony Eugene Karam
Ultrafast And Nonlinear Spectroscopy Of Colloidal Nanomaterials, Tony Eugene Karam
LSU Doctoral Dissertations
In the first part of this dissertation, the adsorption isotherms, resonance coupling, and fluorescence of molecular dyes on the surface of plasmonic nanoparticles are investigates. SHG is also used to investigate the growth of a silver shell on the surface of gold nanoparticles in real time. Additionally, gold-silver-gold core-shell-shell nanoparticles possess extinction peak wavelengths that can be controlled over the visible and near-infrared regions and enhanced photothermal effect. Transient absorption measurements determine that the phonon-phonon scattering lifetime is considerably faster in the core-shell-shell nanoparticles than in the gold nanospheres and gold nanorods, which contributes to the higher photothermal efficiencies. Transient …
Contemporary Organic Transformations Enabled By Novel Cationic Processes, Caitlan Elizabeth Ayala
Contemporary Organic Transformations Enabled By Novel Cationic Processes, Caitlan Elizabeth Ayala
LSU Doctoral Dissertations
This dissertation focuses on the development of synthetic methodologies in organic synthesis in two different areas. Chapter 1 discusses the more recent examples of transforming alcohols to their corresponding alkyl chlorides. The first area of our group’s research interest is the development of a mild chlorination method from unactivated alcohols, detailed in Chapter 2. Chapter 3 provides an insight into the history of oxyallyl cations, the basis of the second methodology development project in our laboratory. This chapter focuses on the traditional reactions that utilize these reactive intermediates, and it also showcases the concept of direct nucleophilic addition and the …
Fundamental Studies Of Humic Acid's Influence On Pollutant Toxicity To Aquatic Organisms, Rachel Dawn Deese
Fundamental Studies Of Humic Acid's Influence On Pollutant Toxicity To Aquatic Organisms, Rachel Dawn Deese
LSU Doctoral Dissertations
The main purpose of the research presented in this dissertation was to further understand the intricate and convoluted interactions between natural organic material, biological entities, and pollutants. This was achieved by utilizing humic acids (HAs) from differing sources, chemically modified humic acid, two biological entities (model biomembranes and Artemia Franciscana), and three types of pollutants (cations, surfactants, and carbon nanotubes). Fluorescence spectroscopy and model biomembranes were used to measure the change in HA’s ability to interact with the biomembranes in the presence of cations. Three differently sourced HAs, chemical modified HAs, and a range of cations were studied to elucidate …
Understanding Chemical Reactions In Novel Materials: From Metal Organic Frameworks To Oxyallyl Cations, Kiara Taylor-Edinbyrd
Understanding Chemical Reactions In Novel Materials: From Metal Organic Frameworks To Oxyallyl Cations, Kiara Taylor-Edinbyrd
LSU Doctoral Dissertations
The work of this dissertation investigates the chemical processes of novel materials through quantum mechanical calculations and molecular dynamics simulations. The first section of this work focuses on probing copper based metal organic frameworks (MOFs) for their ability to catalytically release nitric oxide from s-nitrosothiol (RSNO) precursors in a slow, controlled and sustained manner and compares these findings to a free copper ion/ethanol solution. Through the use of electronic structure calculations and molecular dynamics simulations, studies are carried out to better understand how the barriers of RSNOs approach to the catalytic copper center changes with modifications to the R-group (of …
An Investigation Of Environmentally Persistent Free Radical (Epfr) Formation In Contaminated Soils Using Surrogate-Based Model Systems, Ugwumsinachi Godwin Nwosu
An Investigation Of Environmentally Persistent Free Radical (Epfr) Formation In Contaminated Soils Using Surrogate-Based Model Systems, Ugwumsinachi Godwin Nwosu
LSU Doctoral Dissertations
Environmentally persistent free radicals (EPFRs) have recently attracted attention due to their properties that detrimental to the health of living organisms. Earlier studies devoted to the formation of combustion generated particulate matter (PM) showed that EPFRs formed as a result of the association of aromatic chlorinated hydrocarbons with transition metal centers. Based on our previous studies, the amounts of EPFRs formed at Superfund soil sites contaminated with pentachlorophenol (PCP) are ~30 times higher compared to those formed at the neighboring uncontaminated soil sites, showing that EPFR formation is not confined to combustion generated particle. In order to design viable remediation …
Investigating The Structure Of The Papain-Inhibitor Complex Using Spr And Nmr, Margaret Sara Thomasson
Investigating The Structure Of The Papain-Inhibitor Complex Using Spr And Nmr, Margaret Sara Thomasson
LSU Doctoral Dissertations
Cysteine proteases (CPs) are enzymes with a nucleophilic thiol in their active sites. Inhibitors of cysteine proteases (ICPs) occur naturally in bacterial pathogens and some protozoa. In parasites, ICPs are often virulence factors, contributing to the formation and survival of amastigotes within host cells. These amastigotes have higher CP activity, therefore making both ICPs and CPs potential drug targets. Despite great genetic variability, ICPs contain highly conserved structural features, including a series of defined loops that play a significant role in binding CPs. Papain, a CP from Carica papaya, complexes with ICP from Leishmania mexicana. Although the individual 3-D structures …
Time-Lapse Polymerizations Triggered By Ph Clock Reactions, Elizabeth Jee
Time-Lapse Polymerizations Triggered By Ph Clock Reactions, Elizabeth Jee
LSU Doctoral Dissertations
The theme of this work is time-lapse polymerizations triggered by pH clock reactions. The first chapter is the introduction and gives a long overview of the different chemistries studied here. The second chapter focuses on the bromate-sulfite clock reaction. Based on some simplified and accepted reaction equations for the bromate-sulfite clock. We presumed it may be possible to increase the pH of the solution via ammonia addition and hinder or significantly reduce the reactivity of the clock reagents, thus creating a storage stable reaction. Adding a polymer system that would not crosslink until the solution became acidic would have created …
Biomedical Applications Of Thiol-Acrylate Polymers, Leah Alyce Garber
Biomedical Applications Of Thiol-Acrylate Polymers, Leah Alyce Garber
LSU Doctoral Dissertations
The development of biocompatible polymers using thiol-acrylate Michael addition reactions between not only acrylates and thiols but also between amines and acrylates were demonstrated. The synthesis of an in situ tertiary amine catalyst initiates the propagation steps of the polymerization process by subsequently reacting with trimethylolpropane tris (3-mercaptopropionate) (TMPTMP). A few notable characteristics of this reaction are tunable gel times, the capability of reaching high polymer conversion and suitable mechanical strength. With addition of hydroxyapatite to the polymeric phase and foaming, a porous bone composite was produced. Further osteogenisis and in vivo work using the PETA-co-TMPTMP (HA) composite material was …
Visible Light And Electron Transfer Chemistry For O-Glycosylation And Remote Hydroxylation, Mark Louis Spell
Visible Light And Electron Transfer Chemistry For O-Glycosylation And Remote Hydroxylation, Mark Louis Spell
LSU Doctoral Dissertations
This dissertation focuses on the synthesis of dauer pheromone analogs for biological evaluation, the development of visible light promoted O-glycosylation methods and the development of an Ir(ppy)3 catalyzed C-H hydroxylation method. Chapter 1 describes the synthesis of dauer pheromone analogs. C.elegans is a small nematode that enters a dauer stage when encountering unfavorable environmental conditions. The dauer stage is initiated by the nematodes chemosensation of the dauer pheromone caused by the down regulation biochemical pathways TGF-â and IGF-1. These biochemical pathways are also seen in Homo Sapiens and play a role in a number of biological processes. Understanding how these …
Molecularly Imprinted Polymers For Enantiomer Separations And Biomolecular Sensors, Britney Lyn Hebert
Molecularly Imprinted Polymers For Enantiomer Separations And Biomolecular Sensors, Britney Lyn Hebert
LSU Doctoral Dissertations
Molecularly Imprinted Polymers (MIPs) encompass a wide range of applications by changing the different components, e.g. the template, crosslinker or functional monomers. Of interest among these different applications are separations and sensors. Separations by MIPs traditionally use a chiral pure template but in some cases that chiral pure template may not be available for imprinting. Using chiral (N-α-bismethacyloyl-L-alanine) and achiral (N,O-bisacrylamide ethanolamine) crosslinkers we investigated imprinting of scalemic and racemic template mixtures of Boc-tyrosine enantiomers. The achiral and chiral crosslinkers yielded similar results for the partial separation of enantiomers by scalemic imprinted polymers because separation and recognition are not dependent …
Synthetic Efforts Towards The Synthesis Of Prostaglandin Pgf2a, Amy Marie Pollard
Synthetic Efforts Towards The Synthesis Of Prostaglandin Pgf2a, Amy Marie Pollard
LSU Doctoral Dissertations
This dissertation describes strategies for synthesizing prostaglandin PGF2α. Our synthetic design creates the stereochemistry needed for the core and side chains of the target prostaglandin PGF2 alpha and PGF2 alpha synthase selective analogues while incorporating iodocyclization desymmetrization of acyclic dienes. A model system for 4-(iodomethyl)-6-methyl-1,3-dioxan-2-one was developed and synthesized for our target compound 4-(2-(benzyloxy)ethyl)-6-(iodomethyl)-5-vinyl-1,3-dioxan-2-one. Both compounds were successfully synthesized providing useful stereocenters for completing the synthesis of prostaglandin PGF2 alpha. Efforts toward total stereochemical control of PGF2α include the partial syntheses of bis-diethylanimedimethylsilane and of (4S,5S)-2-((1E,3E)-penta-1,3-dien-1-yl)-4,5-diphenyl-1,3-ditosyl-1,3,2-diazaborolidine.
Thiol-Acrylate Polymerization Kinetics And Applications In Microfluidics, Michael Perrin Tullier
Thiol-Acrylate Polymerization Kinetics And Applications In Microfluidics, Michael Perrin Tullier
LSU Doctoral Dissertations
The reaction kinetics and some applications in the field of microfluidics for thiol-acrylate Michael addition polymerizations using multifunctional monomers have been researched and are presented here. The polymerization rate constants for base-catalyzed systems were found to increase with increasing thiol and acrylate functionality, which was attributed to the intramolecular interactions between functional groups. The nucleophile-initiated thiol-acrylate Michael addition polymerization kinetics were monitored via FTIR, and it was determined that the increase in the rate of reaction in these multifunctional systems was significantly less dramatic than the increase observed in monofunctional systems. While no radical polymerization was observed during most typical …