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LSU Doctoral Dissertations

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Full-Text Articles in Chemistry

Use Of X-Ray K-Edge Tomography And Interferometry Imaging Techniques For The Studies Of Brominated Flame Retardants, Mutairu Bolaji Olatinwo Jan 2016

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 …


Synthetic Efforts Towards The Synthesis Of Prostaglandin Pgf2a, Amy Marie Pollard Jan 2016

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.


Ultrafast And Nonlinear Spectroscopy Of Colloidal Nanomaterials, Tony Eugene Karam Jan 2016

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 …


Synthesis Of Functional Polypeptides And Development Of New Synthetic Strategies Toward Polypeptides, Jinbao Cao Jan 2016

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 …


Time-Lapse Polymerizations Triggered By Ph Clock Reactions, Elizabeth Jee Jan 2016

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 …


Design And Implementation Of Qcm Virtual Sensing Schemes For Analyses Of Volatile Organic Compounds, Nicholas Colby Speller Jan 2016

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 …


Visible Light And Electron Transfer Chemistry For O-Glycosylation And Remote Hydroxylation, Mark Louis Spell Jan 2016

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 …


Thin Films Of Semiconducting Polymers And Block Copolymers By Surface-Initiated Polymerization, Sang Gil Youm Jan 2016

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 …


Hybrid Inorganic Core- Conjugated Polymer Shell Nanoparticles Prepared By Surface-Initiated Polymerization, Sourav Chatterjee Jan 2016

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. …


Computational Studies On Bimetallic Catalysis And X-Ray Absorption Spectroscopy, Sayakkarage R. G. Fernando Jan 2015

Computational Studies On Bimetallic Catalysis And X-Ray Absorption Spectroscopy, Sayakkarage R. G. Fernando

LSU Doctoral Dissertations

Computational studies are very important to gain an insight into reaction mechanisms and in interpreting and understanding complicated experimental observations. This report contains a discussion on computational studies performed on bimetallic catalysis and on X-ray absorption spectroscopy of insulators. The viability of a bimetallic rhodium and cobalt catalysts for industrially important hydroformylation and aldehyde-water shift catalysis (AWS) is discussed. Density functional theory (DFT) studies were used for bimetallic catalysis and time-dependent DFT studies were used for excited state dynamics. These studies were performed using Gaussian 09 package and NWChem. Hydroformylation is experimentally performed in acetone and 30% water/acetone systems and …


Platinum Complexes With Tridentate Ligands As Models For Active Monofunctional Anticancer Drugs, Chase Koby Andrepont Jan 2015

Platinum Complexes With Tridentate Ligands As Models For Active Monofunctional Anticancer Drugs, Chase Koby Andrepont

LSU Doctoral Dissertations

Pt(II) complexes bind preferentially at N7 of G residues of DNA, causing DNA structural distortions associated with anticancer activity. Some distortions induced by difunctional cisplatin are also found for monofunctional Pt(II) complexes with carrier ligands having bulk projecting toward the guanine base. This ligand bulk can be correlated with impeded rotation about the Pt–N7(guanine) bond. The objective of this study is to understand the influences of in-plane bulk of Pt(Ltri)G adducts (Ltri = tridentate carrier ligand, G = guanine derivative bound to a metal, but not tethered to another nucleobase). NMR spectroscopy provided conclusive evidence that Pt(Ltri)G (Ltri = di-(2-picolyl)amine …


The Electronic Structure Of Environmentally Persistent Free Radicals Formed On Metal Oxide Surfaces, Chad Allen Thibodeaux Jan 2015

The Electronic Structure Of Environmentally Persistent Free Radicals Formed On Metal Oxide Surfaces, Chad Allen Thibodeaux

LSU Doctoral Dissertations

We have investigated the electronic structure of environmentally persistent free radicals (EPFRs) formed on two different metal oxides: Cu(II)O and ZnO. Cu(II)O is known to be one of the most active metal oxides to form EPFRs. ZnO, however, forms the longest-lived EPFRs. First, we examined the adsorption of phenol on different crystal faces of ZnO. Ultraviolet photoelectron spectroscopy (UPS) shows direct evidence of charge transfer away from the ZnO to the phenol. This differs from the hypothesized mechanism of EPFR formation that says that an electron is transferred to the metal oxide. UPS difference spectra also shows that the phenol …


Synthetic Methods Development Towards The Total Synthesis Of Chlorosulfolipids, Andres Villalpando Jan 2015

Synthetic Methods Development Towards The Total Synthesis Of Chlorosulfolipids, Andres Villalpando

LSU Doctoral Dissertations

The focus of this dissertation is the development of a novel chlorination reaction utilizing a triphosgene-amine based mixture towards the total synthesis of chlorosulfolipids, a subclass of naturally occurring organohalogen natural products. This novel, mild chlorination reaction will be utilized under a global chlorination strategy to chlorinate multiple alcohol substituents in one synthetic operation. Chapter one details the history of chlorosulfolipids from the early stages of their isolation, relevant structural elucidation techniques, appropriate biosynthetic discoveries, and their biological relevance to a thorough investigation of the total syntheses completed to date. These compounds demonstrate a range of biological activities and have …


Chemically Patterned Surfaces As Test Platforms To Study Magnetic And Solvent-Responsive Properties At The Nanoscale: Investigations Using Scanning Probe Microscopy, Shalaka Kulkarni Jan 2015

Chemically Patterned Surfaces As Test Platforms To Study Magnetic And Solvent-Responsive Properties At The Nanoscale: Investigations Using Scanning Probe Microscopy, Shalaka Kulkarni

LSU Doctoral Dissertations

Chemically patterned surfaces were fabricated using a combination of molecular self-assembly and particle lithography to generate billions of nanostructures of organosilane self-assembled monolayers (SAMs). Monodisperse mesospheres were used as surface masks to prepare nanostructures on flat surfaces using the simple benchtop chemistry steps of mixing, centrifuging, evaporation, and drying. Periodic arrays of well-defined organosilane nanostructures serve as discrete surface sites for the selective deposition of polymers and magnetic nanoparticles.

In this dissertation, particle lithography approaches for surface patterning provide new directions for studying surface chemistry at the molecular-level using high resolution investigations with scanning probe microscopy (SPM). Atomic force microscopy …


Method Development For The Assignment Of Nmr Peaks And The Determination Of Quaternary Protein Structure Using Reductive Methylation, Pamlea Nicole Brady Jan 2015

Method Development For The Assignment Of Nmr Peaks And The Determination Of Quaternary Protein Structure Using Reductive Methylation, Pamlea Nicole Brady

LSU Doctoral Dissertations

The work described herein is centered on reductive methylation, a chemical modification reaction, which allows for the introduction of methyl groups at the primary amines of the lysine side chain and at the N-terminus. The resulting methyl groups are effective probes for the study of protein structure and dynamics using nuclear magnetic resonance spectroscopy (NMR). Described herein is work conducted on the development of tools for the study of protein structure using reductive methylation, highlighting options for addressing limitations of the labeling method encountered by its practical use. Chapter 1 serves as a brief introduction to protein structure and the …


Investigating The Photorecombination Dynamics In Molecular High-Harmonic Spectra, Benjamin Parker Wilson Jan 2015

Investigating The Photorecombination Dynamics In Molecular High-Harmonic Spectra, Benjamin Parker Wilson

LSU Doctoral Dissertations

The work presented in this dissertation will relate the photorecombination dynamics to photoionization dynamics in SF6 utilizing the self-probing mechanism, high harmonic generation (HHG). This work specifically aims to establish parameters for which the comparison is applicable and the macroscopic complications inherent in HHG do not interfere with the extraction of dynamic information. The first part of this work established the macroscopic experimental apparatus necessary for consistent spectroscopic observation. It is shown that using a gas jet that is an order of magnitude shorter than the Rayleigh length of the driving laser results in more consistent harmonic spatial profiles and …


Development Of Transition Metal-Catalyzed Polymerization Reactions And Their Applications For The Preparation Of Well-Defined Conjugated Polymer Architectures, Carlos Anthony Chavez Jan 2015

Development Of Transition Metal-Catalyzed Polymerization Reactions And Their Applications For The Preparation Of Well-Defined Conjugated Polymer Architectures, Carlos Anthony Chavez

LSU Doctoral Dissertations

The synthesis of conjugated polymers and design of complex materials based on them have become increasingly popular as the demand for low-cost efficient and processible optoelectronic and semiconducting devices escalates. While advanced applications of polymeric materials require some degree of sophistication, success can be achieved through careful consideration of polymerization techniques and methodologies. Controlling critical aspects of the polymerization process allows for synthesis of complex macromolecular architectures possessing unique and novel properties that may be worth of further comprehensive investigation. This dissertation primarily focuses on the development and preparation of well-defined hierarchical macromolecular architectures. The foundation of this work encompasses …


Development Of New Linking Chemistry With The Fac-{Re(Co)3}+ Core For Eventual Applications In Radiopharmaceuticals In Imaging And Therapy, Aponsu Meregngna Pramuditha Lakmi Abhayawardhana Jan 2015

Development Of New Linking Chemistry With The Fac-{Re(Co)3}+ Core For Eventual Applications In Radiopharmaceuticals In Imaging And Therapy, Aponsu Meregngna Pramuditha Lakmi Abhayawardhana

LSU Doctoral Dissertations

The facile labeling of biomolecules with a radionuclide is a key goal in radiopharmaceutical development. This study explores two different ligand systems for fac-[Re(CO)3L]+ complexes, that could be used in bioconjugation. The first approach uses a tridentate ligand having a sulfonamide linkage and modeled on previously evaluated fac-[Re(CO)3(N(SO2R)dpa)]PF6 complexes. The present goal was to develop new related sulfonamide complexes with more hydrophilic ligands designed to avoid the bioavailability problems that would plague the N(SO2R)dpa ligand system. A series of fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes with different R groups linked to the central nitrogen of a symmetric tridentate sulfonamides were synthesized with the aim …


A Monte Carlo Approach To Studying The Hydrogen Storage Capabilities Of Potassium Magnesium Hydride (Kmgh3), Brandon L. Borill Jan 2015

A Monte Carlo Approach To Studying The Hydrogen Storage Capabilities Of Potassium Magnesium Hydride (Kmgh3), Brandon L. Borill

LSU Doctoral Dissertations

Grand Canonical Monte Carlo (GCMC) simulations and the weighted histogram analysis method (WHAM) were employed at selected temperatures and pressures in the study of the hydrogen storage capabilities of KMgH3. A specially tailored addition/removal algorithm was employed to add hydrogen directly at the lattice sites. Agreement between experimental results was obtained through GCMC simulations. WHAM type studies were employed to obtain probability distributions for the purpose of learning the probability of finding hydrogen atoms at specific temperatures and hydrogen pressures. The radial distribution function was employed to study the changes in the structure of KMgH3 for the selected model as …


Synergistic Properties-Driven Synthesis Of Aluminides, Antiomonides, And Bioceramics, Pilanda Watkins-Curry Jan 2015

Synergistic Properties-Driven Synthesis Of Aluminides, Antiomonides, And Bioceramics, Pilanda Watkins-Curry

LSU Doctoral Dissertations

The synthesis, characterization, and properties of selected intermetallics and ceramic materials are presented in this dissertation. In our quest to grow single crystal intermetallics from the metal flux technique, new strategies were employed to avoid thermodynamically stable phases and to ensure sample homogeneity of the crystalline product for structure elucidation and accurate measurements of their magnetic and electrical properties. The relationship between the complex crystal structures and magnetic properties are reported for LnCo2Al8 (Ln = La-Nd, Sm, Yb), CeCo2-xMnxAl8 (0 < x < 1), and Pr2Fe4-xCoxSb5 (1 ≤ x < 3). The discovery of magnetic frustration in LnCo2Al8 (Ln = Ce, Nd) and complex magnetic ordering coupled with large positive magnetoresistance of up to 150% and 60% at 200 K with relatively low field of H = 1 T in Pr2Fe4-xCoxSb5 (x ≈ 2 and 2.5) is also reported. The demand of new inorganic solid materials as scaffolds for the engineering of bone tissue has led to the synthesis of calcium magnesium silicates such as, diopside (CaMgSi2O6), akermanite (Ca2MgSi2O7), monticellite (CaMgSiO4), and merwinite (Ca3Mg(SiO4)2)) for studying dimensionality and mechanical properties. This dissertation highlights the synergism of solid state chemistry at the interface of condensed matter physics and biological engineering. The discovery of compounds with tunable magnetic, electrical, and mechanical properties will be described herein.


I. Synthesis Of Ascarosides For Chemical Biology Studies In Caenorhabditis Elegans, Ii. A Photochemical Approach To Delavayine, And Iii. Remote Hydroxylation By Radical Translocation And Polar Crossover, Kyle Allen Hollister Jan 2015

I. Synthesis Of Ascarosides For Chemical Biology Studies In Caenorhabditis Elegans, Ii. A Photochemical Approach To Delavayine, And Iii. Remote Hydroxylation By Radical Translocation And Polar Crossover, Kyle Allen Hollister

LSU Doctoral Dissertations

The foci of this dissertation are the synthesis of analogs for chemical biology studies, synthetic chemistry method development (with an emphasis on photochemistry), and the application of these methods toward total synthesis. Chapter 1 outlines the synthesis of an array of pheromone analogs that are derivatives of the dideoxy sugar ascarylose. Referred to as ascarosides, such compounds have recently been shown to influence important biological processes in the model organism Caenorhabditis elegans. C. elegans secretes ascarosides into its environment, where the compounds then act as signaling molecules by providing information on factors like population density. Chapter 2 describes the biological …


Nanoscale Gumbos: Size-Control, Characterization, And Applications As Enantioselective Molecularly Imprinted Polymers And Fluorescent Materials, Suzana Hamdan Jan 2015

Nanoscale Gumbos: Size-Control, Characterization, And Applications As Enantioselective Molecularly Imprinted Polymers And Fluorescent Materials, Suzana Hamdan

LSU Doctoral Dissertations

Nanomaterials derived from a group of uniform materials based on organic salts (GUMBOS) have been introduced into the scientific literature through many analytical, biological, and technological applications. These nanomaterials, referred to as nanoGUMBOS, have been shown to display a number of interesting properties including fluorescence, magnetism, tumor targeting, and optoelectronic properties. Herein, we present major studies on nanoGUMBOS including synthesis and size-control, chiral molecular imprinting in polymers, as well as investigation of optical properties and quantum yield of fluorescent semiconductor-based nanoGUMBOS. Various strategies were introduced for production of well-defined nanoGUMBOS. Specifically, several methods based on sonochemistry, microwave, cyclodextrin, and surfactant-assisted …


I. Synthesis Of Ascarosides For Biological Evaluation And Ii. Development Of Visible Light-Promoted Selenofunctionalization And Grafting Of Aryl Iodides, Elizabeth Susan Conner Balapitiya Jan 2015

I. Synthesis Of Ascarosides For Biological Evaluation And Ii. Development Of Visible Light-Promoted Selenofunctionalization And Grafting Of Aryl Iodides, Elizabeth Susan Conner Balapitiya

LSU Doctoral Dissertations

This dissertation focuses on analog synthesis for biological evaluation and visible light promoted method development. Chapter 1 centers upon the synthesis of Caenorhabditis elegans dauer pheromone analogs. C. elegans is a nematode which, in times of environmental stress, enters a dauer stage. Two highly conserved pathways, which play important roles in some diseases in higher organisms, monitor dauer formation: TGF-β and IGF-1. Dauer formation is triggered by the nematode’s chemosensation of the dauer pheromone, consisting of a group of previously-isolated ascarosides. These compounds differ in chain length, saturation, terminal functionality of side chain, ω vs. ω-1 oxygenation and presence of …


Photoelectrons And Recombining Electrons In Atomic And Molecular Systems, Kristen D'Ann Fulfer Jan 2015

Photoelectrons And Recombining Electrons In Atomic And Molecular Systems, Kristen D'Ann Fulfer

LSU Doctoral Dissertations

This work in this dissertation explores how photoelectrons enter and exit atoms and molecules. The electron rescattering events which may occur during photoionization or photorecombination processes play a dominant role in the understanding of how photoelectrons enter and exit molecules, which is intrinsically linked to how chemical reactions occur. Chapters 3-4 of this dissertation present evidence of vibrational mode specific breakdown of the Franck-Condon Principle in the photoionization of low symmetry molecules, acrolein and the singly halogenated thiophenes, due to resonant and non-resonant electron rescattering dynamics. In Chapters 5-6, the disentanglement of the valence electronic structure, as well as evidence …


Gumbos As Matrices For Matrix-Assisted Laser Desorption Ionization Time Of Flight Mass Spectrometry, Hashim Abdullah Al Ghafly Jan 2015

Gumbos As Matrices For Matrix-Assisted Laser Desorption Ionization Time Of Flight Mass Spectrometry, Hashim Abdullah Al Ghafly

LSU Doctoral Dissertations

This work involves the investigation of a group of uniform materials based on organic salts (GUMBOS) as matrices for matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF) for analysis of hydrophobic biomolecules. GUMBOS are new class of materials that show great promise as MALDI matrices because they are able to form a thin-layer on the MS target, thereby enhancing the sample homogeneity, signal intensity, and shot-to-shot reproducibility. The detection of hydrophobic peptides using MALDI-TOF MS remains a challenge because the majority of matrices utilized are hydrophilic thereby exhibiting low affinity for hydrophobic molecules. To address this, I …


Single Molecule Electrophoresis And Optical Detection Using Thermoplastic Nanofluidic Devices: An Experimental And Simulation Study, Kumuditha Madushanka Weerakoon Ratnayake Jan 2015

Single Molecule Electrophoresis And Optical Detection Using Thermoplastic Nanofluidic Devices: An Experimental And Simulation Study, Kumuditha Madushanka Weerakoon Ratnayake

LSU Doctoral Dissertations

Nanofludic devices provide a great platform for single molecular analysis. The unique phenomena in nanoscale gained such interest in investigating the single molecular behavior in nanochannels. Sizes less than 200 nm in one or two-dimensional structures have lead to fascinating observations not accessible in microscale. When a single molecule translocates through a nanotube it interacts with channel walls by adsorption/ desorption, van der Waals interactions and hydrophilic interactions providing a mechanism for separation without any extra additives. Moreover, double layer thickness governed by the background electrolyte plays a vital role. We report single molecular electrophoresis phenomena in nanochannels and nanoslits …


Synthesis, Characterization, And Evaluation Of Small Molecule-Based Fluorogenic Probes For The Detection Of Cellular Thiols, Rasika Ranatunga Nawimanage Jan 2015

Synthesis, Characterization, And Evaluation Of Small Molecule-Based Fluorogenic Probes For The Detection Of Cellular Thiols, Rasika Ranatunga Nawimanage

LSU Doctoral Dissertations

Fluorescence methods for disease diagnosis and detection of important analytes are becoming popular route as a technique, as they offer a simple non-invasive approach. Recently, many novel fluorophores and probes have been reported for selectively and sensitively detecting low abundance biological species in disease pathways. Biological thiols, such as glutathione, cysteine, and homocysteine, along with the smallest member hydrogen sulfide, are key thiol analytes in biological environments, and they play a vital role in living systems by maintaining the redox homeostasis of cells. Alteration of their ratios can cause cellular dysfunction and cell death. Furthermore, thiol levels in cells and …


Design And Application Of Task-Specific Organic Salts For Chemical And Biochemical Sensing, Waduge Indika Subodha Galpothdeniya Jan 2015

Design And Application Of Task-Specific Organic Salts For Chemical And Biochemical Sensing, Waduge Indika Subodha Galpothdeniya

LSU Doctoral Dissertations

There is an increasing demand for development of new sensors and sensor strategies for accurate detection and discrimination of various analytes. In this regard, colorimetric and fluorometric sensor approaches have attracted considerable attention, primarily because they represent facile and inexpensive analytical tools. In this dissertation, I discuss the design and application of sensors and sensor arrays using task specific organic salts: ionic liquids (ILs) and a group of uniform materials based on organic salts (GUMBOS). As compared to typical ionic compounds, these two classes of organic salts exhibit relatively lower melting points due to bulky organic cations and/or anions. Interestingly, …


Scanning Probe Investigations Of Nanopatterned And Thermo-Responsive Polypeptoids And The Design Of A Sample Stage For Force Modulation Microscopy, Lu Lu Jan 2015

Scanning Probe Investigations Of Nanopatterned And Thermo-Responsive Polypeptoids And The Design Of A Sample Stage For Force Modulation Microscopy, Lu Lu

LSU Doctoral Dissertations

Protocols for patterning nanostructures of polymers were developed to enable scanning probe microscopy (SPM) studies of surface properties at the molecular level. A chemically selective surface for patterning polymers was generated by combining particle lithography with organosilane immersion. Poly(N-allyl glycine), a biocompatible and backbone degradable polypeptoid, was grown on Si(111) at confined amine sites using surface-initiated polymerization (also known as the “graft from” approach). A thermo-responsive random copolypeptoid, poly[(N-ethyl glycine)32-r-(N-butyl glycine17)], was pre-synthesized and attached onto a patterned organosilane surface using a thiol-ene click reaction (“graft to” approach). The phase transitions of the copolypeptoid nanostructures in an aqueous environment was …


Boron Functionalization Of Bodipy Dyes, And Their Evaluation As Bioimaging Agents, Alex Long Nguyen Jan 2015

Boron Functionalization Of Bodipy Dyes, And Their Evaluation As Bioimaging Agents, Alex Long Nguyen

LSU Doctoral Dissertations

BODIPY, also known as “porphyrin’s little sister,” belongs to a class of fluorescent dyes. It contains a dipyrromethene π-system with a disubstituted boron atom. The basic 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) is known for its numerous useful applications in the fields of biology and materials. Modification of this well-known fluorophore has been shown to change its photophysical and chemical properties. There has been great interest in the modification at the boron center in recent years for synthesizing new dyads and cascade-type dyes. This work focuses on functionalization at the boron center with carbon and oxygen nucleophiles for further investigation as bioimaging agents. Chapter …