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Liquid Sorption Properties And Structural Changes Of Metal-Organic Frameworks Of Cobalt Nitrate And 4,4'-Bipyridine, Kathryn Mauger-Sonnek

Dissertations and Theses @ UNI

Metal-organic frameworks consist of metal ions connected by organic ligands. When the metal ions and organic ligands link together in the right geometry, polymeric and infinite 1D chains or 2D and 3D networks are formed. Porous metal-organic frameworks were synthesized from the organic ligand 4,4′-bipyridine (bpy) and cobalt(II) nitrate. The metal-organic frameworks synthesized in this study grew into both a previously known 2D bilayer structure, [Co2(bpy)3(NO3)4]n, and a new, orange 1D chain structure, [Co(bpy)NO3)2(H2O)2]n, within ethanol. It was found that the presence of water was the main factor of causing formation of the orange 1D chain crystals. Drying the orange …

Detection Of Microorganisms Using Maldi And Ion Mobility Mass Spectrometry, Juaneka Monet Hayes

LSU Doctoral Dissertations

Matrix-assisted laser ablation desorption ionization MALDI and ion mobility (IM) MALDI mass spectrometry (MS) were used for the detection and identification of microorganisms. MALDI MS is an analytical tool that separates ions by their mass-to-charge ratio (m/z) and is routinely used for bioanalysis because of its sensitivity, selectivity, general applicability, and tolerance to impurities. Ion mobility is a gas phase technique that separates ions based on their charge and collision cross-section. In this research, MALDI-TOF MS and MALDI-IM-TOF MS analysis were conducted in parallel to assess the effectiveness of MALDI-IM-TOF MS for microorganism identification. Whole cell bacteria Escherichia coli strain …

Structural And Synthesis Studies Of The Pro¹⁴³ Region Skp1 In Dictyostelium Discoideum, Chamini V. Karunaratne

LSU Doctoral Dissertations

In Skp1 of Dictyostelium discoideum (Dd), Pro143 is located at the N-terminus of an α-helix with four consecutive Glu residues immediately following Pro. Preceeding Pro143 is a segment of random coil. The proline residue undergoes post-translational modifications: hydroxylation and glycosylation. A cytoplasmic prolyl hydroxylase (P4H1) delivers a hydroxyl group to Pro143 and N-acetylglucosamine transferase 1 (Gnt1) transfers GlcNAc from UDP to Hyp143 of Skp1. The installation of the first GlcNAc residue in Skp1 in Dictyostelium is important for the organism to differentiate into a fruiting body to disperse spores. We describe herein some structural and synthesis studies of the Pro143 …

Amplifying Conjugated Polymers For Fluorescent Chemosensing, Deepa Pangeni

LSU Doctoral Dissertations

Chemo- and biosensors based on fluorescent conjugated polymers 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. In the conventional sensor design paradigm, excitons migrate from the bulk of the polymer to the analyte binding sites which can be either fluorescence quenching sites (turn-off sensors) or lower energy fluorophores (turn-on sensors). In this dissertation, we proposed an alternative design paradigm when analyte binding creates a higher energy gap site in the polymer backbone. In the case of isolated polymer chains in dilute solution, …

Scanning Probe Investigations Of The Surface Self-Assembly Of Organothiols And Organosilanes Using Nanoscale Lithography, Tian Tian

LSU Doctoral Dissertations

Particle lithography and scanning probe lithography were applied to study the kinetics and mechanisms of surface self-assembly processes. Organothiols on Au(111) and organosilane on Si(111) were chosen as model systems for investigations at the nanoscale using atomic force microscopy (AFM). Fundamental insight of structure/property interrelationships and understanding the properties of novel materials are critical for developments with molecular devices. Methods using an AFM probe for nanofabrication have been applied successfully to prepare sophisticated molecular architectures with high reproducibility and spatial precision. The established capabilities of AFM-based nanografting were reviewed for inscribing patterns of diverse composition, to generate complicated surface designs …

New Strategies For The Synthesis Of Porphyrinoids, Moses Inyanje Ihachi

LSU Doctoral Dissertations

ABSTRACT Chapter 1 describes the most stable isomer of porphyrin called porphycene. In this chapter photodynamic therapy (PDT) is explained, and the application of porphycenes in PDT is also described. Other biological applications and its uses in catalysis are also summarized here. The general chemical reactions of porphycenes are also explained. Chapter 2 involves the synthesis of pyrroles and bipyrroles. Functionalization of pyrrollic substituents is demonstrated using organometallic coupling reactions like Stille coupling and Grubbs olefin metathesis. The synthesis of divinyl bipyrroles is intended to provide an important precursor to porphycene synthesis via ring closing metathesis using Grubbs catalyst. Chapter …

Microfluidics For The Analysis Of Integral Membrane Proteins: A Top-Down Approach, Katrina Nychole Battle

LSU Doctoral Dissertations

The development of fully automated and high-throughput systems for proteomics is now in demand because of the need to generate new protein-based disease biomarkers. Unfortunately, it is difficult to identify protein biomarkers that are low abundant when in the presence of highly abundant proteins, especially in complex biological samples like serum, cell lysates, and other biological fluids. Membrane proteins, which are in many cases of low abundance compared to cytosolic proteins, have various functions and can provide insight into the state of disease and serve as targets for new drugs making them attractive biomarker candidates. Traditionally, proteins are identified through …

Synthesis Of The Western Hemisphere Of Theonellamide C, Saroj Yadav

LSU Doctoral Dissertations

Theonellamides A-F were isolated from Theonella swinhoei by Fusetani and co-workers. Despite considerable synthetic effort to produce theonellamide F by the Shioiri group in the early 1990’s, the total synthesis of a theonellamide has yet to be reported. We report herein our efforts toward some of the required amino acid residues and construction of the western ring of theonellamide C. We describe the synthesis of an uncoded amino acid, (2S,4R)-ɣ-hydroxy-α-amino adipic acid (Ahad), a building block for theonellamide C. We initially investigated the Corey-Lygo method for the catalytic asymmetric generation of the Cα stereocenter. Unfortunately, the alkylation of glycine benzophenone …

Polymer Microsystems For The Enrichment Of Circulating Tumor Cells And Their Clinical Demonstration, Joyce W. Kamande

LSU Doctoral Dissertations

Cancer research is centered on the discovery of new biomarkers that could unlock the obscurities behind the mechanisms that cause cancer or those associated with its spread (i.e., metastatic disease). Circulating tumor cells (CTCs) have emerged as attractive biomarkers for the management of many cancer-related diseases due primarily to the ease of securing them from a simple blood draw. However, their rarity (~1 CTC per mL of whole blood) makes enrichment analytically challenging. Microfluidic systems are viewed as exquisite platforms for the clinical analysis of CTCs due to their ability to be used in an automated fashion, minimizing sample loss …

Design, Synthesis, And Characterization Of Porphyrin Derivatives For Biological Applications, Raja Gabadage Waruna Eranga Jinadasa

LSU Doctoral Dissertations

Chapter 1 of this Dissertation presents a brief introduction to the basic properties of porphyrins and their derivatives (hydroporphyrins), their abundance and functions in the nature, and their applications in photodynamic therapy. Chapter 2 reports the synthesis, characterization, conformational analysis and cellular studies of novel mono conjugated regioisomers of chlorin e₆ derivatives that are promising photosensitizers for photodynamic therapy. All three regioisomers were synthesized from pheophytin a, which was extracted from the alga Spirulina pacifica. In vitro investigations using human carcinoma HEp2 cells show that the 15²-lysyl regioisomers accumulate the most within cells, and the most phototoxic …

Luminescence Studies : Part I. Lanthanide Nanogumbos Part Ii. Near Infrared Photothermal Nanogumbos, Jonathan Carver Dumke

LSU Doctoral Dissertations

Group of Uniform Materials Based on Organic Salts (GUMBOS) are a class of molten salts that have been focused to be specifically tailored towards applications. Primitively, from Davy to Walden molten salts were desirable for organic synthesis due to the properties. GUMBOS have been synthesized into nanoparticles (nanoGUMBOS) by various methods to be used for lanthanide luminescence and hyperthermal cancer therapeutics. Lanthanide photochemistry has been frequently studied for its high luminescence intensity, narrow emission band, and stable luminescent lifetime decay. Aerosol-derived europium nanoGUMBOS were characterized using electron microscopy (39.5 ± 8.4 nm), XPS, and spectroscopic techniques. Spectroscopic measurements indicated intense …

Silica Polypeptide-Based Colloids: Physical Properties And Novel Materials, Cornelia Rosu

LSU Doctoral Dissertations

The investigation of polypeptide composite particles, PCPs, is described. The production of mesoporous and polycolloid architectures is also addressed. PCPs were prepared by both growing form and grafting to method. They consist of a core made of silica, silica-coated magnetite or silica-coated cobalt. Some of the particles were covalently labeled with fluorescein isothiocyanate. Several polypeptides were chosen for attachment on the core: poly(γ-stearyl-L-glutamate), PSLG, poly(Nε-carbobenzyloxy-L-lysine), PCBL and poly(o-benzyl-L-tyrosine), PBTY. Attachment of a well-characterized alkyne-end terminated PSLG and PCBL to an azide- functionalized particle yielded PCPs with a desired sparse coverage. A blend of techniques such as FTIR, XPS, TEM, HTEM, …

Super-Aptamer Bio-Imprinted Hydrogels : An Investigation Into The Optimization And Characterization Of Cross-Linked Polymeric Materials Displaying Macromolecular Amplified Responses, Nicholas Alexander Gariano

LSU Doctoral Dissertations

It is becoming more important to detect ultra-low concentrations of analytes for biomedical, environmental, and national security applications. Equally important is that new methods should be easy to use, inexpensive, portable, and if possible allow detection using the naked eye. Detection of low concentrations of analytes generally cannot be achieved directly, but requires signal amplification by catalysts, macromolecules, metal surfaces or supramolecular aggregates. The rapidly progressing field of macromolecular signal amplification has been advanced using conjugated polymers, chirality in polymers, solvating polymers and polymerization/depolymerization strategies. The use of molecularly imprinted polymers is ideal for creation of novel sensors to meet …

Surface Studies Of Organic Thin Films Using Scanning Probe Microscopy And Nanofabrication, Venetia Denae Lyles

LSU Doctoral Dissertations

Porphyrins and metalloporphyrins have unique chemical and electronic properties and thus provide useful model structures for nanoscale studies of the role of chemical structure for electronic properties. Porphyrins have been proposed as viable materials for molecular-based information-storage devices, gas sensors, photovoltaic cells, organic light-emitting diodes and molecular wires. The function and efficiency of porphyrins in devices is largely attributable to molecular architecture and how the molecules are self-organized. Modifications of the porphyrin macrocycle, peripheral groups or bound metal ions can generate a range of electrical, photoelectrical or magnetic properties. The conductive properties are greatly influenced at the molecular level by …

Environmentally Persistent Free Radicals (Epfrs) In Pm₂.₅ : Their Contribution To Hydroxyl Radical Formation And Atmospheric Transformation, William Micheal Gehling, Jr.

LSU Doctoral Dissertations

Previous research demonstrated environmentally persistent free radicals (EPFRs) will form on particulate surfaces under combustion conditions (temperature range of 150-400 °C) from reactions of organic precursors with redox-active transition metals. With an understanding of how these EPFRs form, it is necessary to determine how they behave in a natural environment after emission. To better understand this, the nature of EPFRs in ambient PM2.5 under simulated atmospheric conditions was investigated. Ambient PM2.5 samples were collected at a roadside ambient monitoring site near heavy interstate traffic and major industrial activity. The EPFR concentration and general radical structure were determined with EPR spectroscopy. …

Experimental And Computational Studies Of Environmentally Persistent Free Radicals (Epfrs) Formation, Lucy W. Kiruri

LSU Doctoral Dissertations

The first part of the thesis investigates the use of theoretical quantum calculations for the study of EPFRs as the initial and fundamental step in the formation of polychlorinated dibenzo-p-dioxin and dibenzofuran. The computational model comprised of density functionals (B3LYP, PBE1PBE, and M06) and two types of basis set namely: LANL2DZ for all atoms and GEN (LANL2DZ for metals and aug-cc-pVDZ for non-metals). Full mechanisms of EPFRs formation over (CuO)1-8, and aluminum oxide clusters were studied. The most stable intermediates and products have been determined and compared to available experimental data. In case of (CuO)1-8 clusters, the small clusters are …

A Microfluidic Bacteria Culturing Device With Maldi Mass Spectrometry Detection, Pratap Reddy Machavaram Siva

LSU Master's Theses

A novel microfluidic device was developed for bacterial cell culturing using mass spectrometry as the detector. One of the challenges in proteomics is to achieve high sensitivity in the identification of proteins in complex samples with widely varying concentrations. The main limitations for proteomic studies are relatively slow and labor-intensive steps such as cell culturing and protein digestion of small sample quantities. Microfluidics is a promising approach to increase throughput and to reduce the time-consuming steps that are necessary for proteomics. When an analytical detection method is combined with microfluidics it can overcome limitations that are important in the analysis …

Analysis Of Protein Aggregates And Synthetic Nanoparticles Using Capillary Electrophoresis With Light Scattering And Fluorescence Detection, Suresh Chandra Regmi

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to develop capillary electrophoresis (CE) based analysis techniques for the characterization of individual particles including amyloid beta (Aâ) peptide aggregates and to apply these methods to study the aggregation of Aâ peptides. Protein self-assembly into ordered aggregates is a common and important process in normal biological function, but this process is also involved in several diseases. Amyloid beta peptide aggregation is linked to Alzheimer’s disease. Thioflavin T (ThT) has been used as a fluorescent probe for the detection of Aâ aggregation. Based on previous observations of false positive fluorescent signals …

Phase Behavior Of Silica-Polypeptide Hybrid Particles Immersed In Cholesteric Liquid Crystals, Melissa Elizabeth Collins

LSU Doctoral Dissertations

Silica-polypeptide hybrid particles are core-shell colloids. Established synthetic methods ensure uniformly sized cores and provide the ability to have magnetic or fluorescent inclusions. The polypeptide shell is highly functional in its ability to respond to stimuli through changes in shape and formation of ordered phases above certain concentrations or temperatures. This research explores the interactions of hybrid particles mixed with polypeptides dispersed in solution. Depletion theory, which considers mainly entropic interactions between particles, can be used to explain the phase behavior of colloids. Due to the chemical similarities between the polypeptides attached to the surface and those free in solution, …

The Development Of Capillary Electrophoresis Assays To Study Enzyme Inhibition, Sherrisse Kelly Bryant

LSU Doctoral Dissertations

New methods for studying enzymes and enzyme inhibition using capillary electrophoresis (CE) were developed and applied. Because CE is a separation technique, spectral interference is minimized by separation of substrates, products, inhibitors, and sample matrix components. Two types of CE enzyme assays were explored in this dissertation research. The first assay was based on optically gated vacancy capillary electrophoresis (OGVCE) with laser-induced fluorescence detection (LIF). This approach involves periodic photobleaching of fluorescent substrates and products. The initial goal of the study was to develop an assay for adenosine deaminase (ADA). A fluorescent ADA substrate was synthesized; however, the substrate was …

Studies Of Core-Shell Nanogumbos And Liposomal Ionogels, Ashleigh Renee' Wright

LSU Doctoral Dissertations

The work presented in this dissertation is a description of novel core-shell nanomaterials derived from a group of uniform materials based on organic salts (GUMBOS) and the synthesis and characterizations of novel liposomal ionogels (LIGs). These GUMBOS are an extension of ionic liquids (ILs) which are organic salts with melting points between 25 °C and 100 °C. Ionic liquids have high thermal stability, low vapor pressure, and tunable physiochemical and functional properties. All of the properties of ILs are controlled by the chosen cation and anion pair. Similarly to ILs, GUMBOS possess the same qualities; however, they have melting points …

Advancing The Field Of Polypeptoids Through The Synthesis Of Novel Architectures And Thermoresponsive Polymers, Samuel Henry Lahasky

LSU Doctoral Dissertations

Peptidomimetic polymers are an emerging class of polymers that are structurally related to polypeptides. Due to their structural similarities, these polymers can be used to study some of the physical aspects of polypeptides (for example, protein folding). They are also increasingly being used in the fields of biology and drug-delivery. Some members of peptidomimetic polymers include polyacrylamides, polyoxazolines and polypeptoids. Polymer synthesis and characterization has been performed for both polyacrylamides and polyoxazolines, with research dating back to the 1950s and 1980s respectively. Research in the field of polypeptoids has not been as extensive; however, emerging synthetic strategies are allowing for …

Determination Of Copper Speciation, Bioavailability And Toxicity In Saltwater Environments, Tara N. Tait

Theses and Dissertations (Comprehensive)

The speciation of copper plays a strong role in determining bioavailability and toxicity upon copper exposure in marine environments. Specifically, natural organic matter (NOM) can complex with copper, influencing speciation and decreasing bioavailability. The aim of this research was to determine accurate copper speciation values using literature and new techniques and applying the techniques that reflect the most accurate speciation values to investigate the influence of NOM quantity and quality on copper speciation and toxicity. The results from this study will have implications on the development of a marine Biotic Ligand Model (BLM). Free copper was measured using a flow-through …

Treatment Of Reverse Osmosis Brine With Advanced Oxidative Processes For Enhanced Phosphorus Removal, Petrease Patton

Theses and Dissertations (Comprehensive)

Current regulations for sensitive receiving waters are approaching the limit of technology for phosphorus removal and improved methods are required. Existing methods target removal of the orthophosphate form of phosphorus, but to achieve low effluent limits other non-reactive (NRP) forms, such as condensed phosphate and organic phosphorus, must be removed as well. This could be accomplished by developing a quaternary step in wastewater treatment that utilizes reverse osmosis (RO) followed by advanced oxidation processes (AOP) on the produced brine (RO concentrate). The objective during advanced treatment is to convert NRP in the brine to reactive phosphorus for removal by traditional …

Cyclic Block Copolypeptoids : Synthesis, Self-Assembly And Macroscopic Properties, Chang-Uk Lee

LSU Doctoral Dissertations

This dissertation presents the first experimental efforts for synthesizing a new class of peptidomimetic polymers, cyclic block copolypeptoids, studying their self-assembly in dilute solution, and examining their macroscopic properties. Cyclic poly(N-methyl-glycine)-b-poly(N-decyl-glycine) (PNMG-b-PNDG) diblock copolymers were synthesized via sequential, N-heterocyclic carbene (NHC)-mediated ring-opening polymerization of NCA monomers with controlled chain length and compositions. Cryo-TEM shows that PNMG105-b-PNDG10 copolymers in methanol (1 mg/mL) form spherical micelles that organize to form cylindrical micelles over time. The formation of cylindrical micelles is attributed to the crystallization of PNDG chains, as revealed by SAED and microDSC analyses. Cyclic PNMG100-b-PNDG10 copolymers form thermo-reversible, free-standing gels at …

Periplasmic Binding Proteins In Thermophiles: Characterization And Potential Application Of An Arginine-Binding Protein From Thermotoga Maritima: A Brief Thermo-Story, Alessio Ausili, Maria Staiano, Jonathan D. Dattelbaum, Antonio Varriale, Alessandro Capo, Sabato D'Auria

Chemistry Faculty Publications

Arginine-binding protein from the extremophile Thermotoga maritima is a 27.7 kDa protein possessing the typical two-domain structure of the periplasmic binding proteins family. The protein is characterized by a very high specificity and affinity to bind to arginine, also at high temperatures. Due to its features, this protein could be taken into account as a potential candidate for the design of a biosensor for arginine. It is important to investigate the stability of proteins when they are used for biotechnological applications. In this article, we review the structural and functional features of an arginine-binding protein from the extremophile Thermotoga maritima …

Structurally Diverse Hamigerans From The New Zealand Marine Sponge Hamigera Tarangaensis: Nmr-Directed Isolation, Structure Elucidation And Antifungal Activity, A. Jonathan Singh, Jonathan D. Dattelbaum, Jessica J. Field, Zlatka Smart, Ethan F. Woolly, Jacqueline M. Barber, Rosemary Heathcott, John H. Miller, Peter T. Northcote

Chemistry Faculty Publications

The NMR-directed investigation of the New Zealand marine sponge Hamigera tarangaensis has afforded ten new compounds of the hamigeran family, and a new 13-epi-verrucosane congener. Notably, hamigeran F (6) possesses an unusual carbon–carbon bond between C-12 and C-13, creating an unprecedented skeleton within this class. In particular, the structural features of 6, hamigeran H (10) and hamigeran J (12) imply a diterpenoid origin, which has allowed the putative biogenesis of three hamigeran carbon skeletons to be proposed based on geranyl geranyl pyrophosphate. All new hamigerans exhibited micromolar activity towards the HL-60 …

"Molecular Spectroscopy And Dynamics Of Reactive Chemical Intermediates Studied Using Laser Induced Fluorescence (Lif), Single Vibronic Level (Svl) Emission And Resonance Enhanced Multiphoton Ionization (Rempi) Spectrometry.", Lloyd Godfrey Muzangwa

Dissertations (1934 -)

ABSTRACT

"MOLECULAR SPECTROSCOPY AND DYNAMICS OF REACTIVE CHEMICAL INTERMEDIATES STUDIED USING LASER INDUCED FLUORESCENCE (LIF), SINGLE VIBRONIC LEVEL (SVL) EMISSION AND RESONANCE ENHANCED MULTIPHOTON IONIZATION (REMPI) SPECTROMETRY"

Lloyd Muzangwa, B.Sc. (Hons, Biochemistry).

Marquette University, 2013

In the studies of complex chemical processes, it is necessary to postulate mechanisms involving transient intermediates such as radicals, ions, and pre-reactive complexes. The detection and characterization of these intermediates affords in ideal cases determination of the detailed chemical mechanism, which, in turn, can permit the development of rational strategies for removing undesired products and enhancing the yield of the desired species. This dissertation describes …

Molecular Tweezers: Studies Directed Towards The Preparation Of Effective Charge Transport Materials, Khushabu Thakur

Dissertations (1934 -)

ABSTRACT

MOLECULAR TWEEZERS: STUDIES DIRECTED TOWARDS THE PREPARATION OF EFFECTIVE CHARGE TRANSPORT MATERIALS

Khushabu Thakur, B.Sc, M.Sc.

Marquette University, 2013

An important focus of the modern areas of photovoltaics and molecular electronics is to identify molecules or molecular assemblies that can promote effective charge/exciton transport over long distances. In order to be able to exert control and establish necessary structural parameters for reproducible production of self-assembled structures for long-distance charge transport, our laboratory has been actively engaged towards the preparation of a variety of well-defined, cofacially-arrayed polybenzenoid nanostructures in which aromatic donors are cofacially stacked.

Herein, we undertake the design …

Environmentally Green Synthesis Of Thioformamide Derivatives, Ali Ramazani, Sang Woo Joo, Fatemeh Zeinali Nasrabadi

Turkish Journal of Chemistry

Reactions of isocyanides with thioacids in water proceeded smoothly at room temperature and in neutral conditions to afford thioformylamide and thioformamide derivatives in high yields. The reaction proceeded smoothly and cleanly under mild conditions and no side reactions were observed.