Chemistry Commons^™

The Utilization Of Metal-Ligand Cooperativity For Electrocatalytic Reduction And Catalytic Hydration., Steven Cronin

Electronic Theses and Dissertations

Small molecules are building blocks for developing larger materials. These small molecules could be extremely small, such as hydrogen, or larger such as a nitrile, but their impact on the global economy is massive. This dissertation describes a catalyst for three reactions involving small molecules; 1) the hydrogen evolution reaction, 2) the carbon dioxide reduction reaction, 3) nitrile hydration. The catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) use “metal-ligand cooperativity” between the Lewis acid Zn(II) metal ion and an uncoordinated Lewis base nitrogen in the ligand framework to activate substrates. The complex has been analyzed via NMR, UV/Vis, single crystal X-ray crystallography, …

Development Of Computational To Ols To Target Microrna, Luo Song

Dissertations and Theses (Open Access)

MicroRNAs (a.k.a, miRNAs) play an important role in disease development. However, few of their structures have been determined and structure-based computational methods remain challenging in accurately predicting their interactions with small molecules. To address this issue, my thesis is to develop integrated approaches to screening for novel inhibitors by targeting specific structure motifs in miRNAs. The project starts with implementing a tool to find potential miRNA targets with desired motifs. I combined both sequence information of miRNAs and known RNA structure data from Protein Data Bank (PDB) to predict the miRNA structure and identify the motif to target, then I …

Nuclear-Targeted Gold Nanoparticles Enhance The Effects Of Radiation Therapy With And Without Liposomal Delivery, Maureen Aliru

Dissertations and Theses (Open Access)

Less that 10% of pancreatic cancer patients are eligible for curative resection, and clinical trials evaluating chemoradiation in locally advanced patients with unresectable disease have been largely disappointing. New and creative therapeutic approaches are needed to address the unment need for treatment options. The objective of this thesis is to advance radiosensitization of treatment-resistant densely desmoplastic pancreatic cancer using nanoparticles to surmount biological barriers to effective particle distribution for DNA-targeting.

Clinical translation of radiosensitizing nanoparticles has stalled owing to technical challenges. Current strategies to use AuNPs for radiosensitization require large quantities of gold, kilovoltage x-rays, immediate irradiation after intravenous administration, …

Predicting The Hydration Free Energy Of Small Alkanes And Alcohols From Custom, Electronic Structure-Based Force Fields, T. Ryan Rogers

Graduate Theses and Dissertations

Mathematical theories reveal the fundamental physics involved in experimentalphenomena. Computer models of such theories are routinely used to corroborate or explain experiments and predict properties of chemical systems. Therefore, an important effort in computational chemistry is the development of more accurate and efficient chemical models. Current-generation models are only beginning to approach experimental-quality predictions of hydration free energies (HFEs).Using computations of quantum mechanical (QM) forces and classical simulations based on these forces, I investigate models to predict several properties of solutes and solutions. This dissertation is a collection of projects exemplifying methods used to gain insight into chemical systems.

Simulations …

Otolith Age Validation And Microchemical Investigation Of The Northern Stock F Atlantic Black Sea Bass (Centropristis Striata), Elise R. Koob

Graduate Masters Theses

Black sea bass (Centropristis striata) is a demersal marine species that supports extensive commercial and recreational fisheries along the Atlantic coast. A recent expansion into the Gulf of Maine raises questions about this species’ movement and population dynamics in the region. Additionally, the 2016 catch-at-age stock assessment model for the northern stock incorporated a population split at the Hudson Canyon. Though this model better accounts for differences in populations, several issues remain. First, validation of the otolith ageing technique for this stock is incomplete; and, second, the origin of fish that moved into the northern ranges of the Gulf of …

Selective Electrocatalytic Reduction Of Co2 To Co With Iron Nheterocyclic Carbene Complexes And Near-Infrared Absorbance Of Ruthenium(Ii) Photosensitizers Containing A Merocyanine Π-Acceptor, Peter Andrew Catsoulis

Graduate Masters Theses

The catalytic proton-coupled reduction of carbon dioxide into C-1 or “common engine” liquid fuels is currently a highly desirable and green approach to removing anthropogenic CO2 from the atmosphere. The most common approach to this is through electrocatalytic homogeneous reductions utilizing inorganic complexes as catalysts. Current research has moved towards the use of first-row transition metals in catalysts due to their high natural abundances and cheap cost. Iron porphyrin complexes have been vastly studied due to their high product selectivity and turnover frequencies. However, these complexes exhibit short lived activity because of competing reactions in their catalytic cycles, rendering them …

Ph Induced Size Tuning Of Gd2hf2o7:Eu3+ Nanoparticles And Its Effect On Their Uv And X-Ray Excited Luminescence, Santosh K. Gupta, Mitzy A. Penilla Garcia, Jose P. Zuniga, Yuanbing Mao

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Size tunable nanoparticles (NPs) have played an important role in areas of optoelectronics, drug delivery, magnetism and many others. Moreover, designing size-tunable NPs without exposing them to high temperature and long time thermal treatment is highly desirable to make agglomerate- and defect-free NPs. In this work, we have designed Gd2Hf2O7:Eu3+ (GHOE) NPs using the molten-salt synthesis (MSS) method with the precursors made from varying precipitant concentrations (correspondingly the pH of the precipitating solution). The obtained NPs have a decreasing size as the pH of the precipitating solution rises and a defect fluorite structure with a large fraction of Eu3+ ions …

Corn And Soybean Response To Wastewater-Recycled Phosphorus Fertilizers, Shane Ylagan

Crop, Soil and Environmental Sciences Undergraduate Honors Theses

The ability to recycle phosphorus (P) from wastewaters could provide a sustainable, continuous source of P that might also help protect surface water quality from P enrichment. The mineral struvite (MgNH4PO4·6H2O) is an understudied material that can be created from Pcontaining wastewater and has been shown to have agricultural fertilizer value. The objective of this study was to evaluate the effects of electrochemically precipitated struvite (ECST), chemically precipitated struvite (Crystal Green; CG), diammonium phosphate (DAP), monoammonium phosphate (MAP), rock phosphate (RP), and triple super phosphate (TSP) on corn (Zea mays) and soybean (Glycine max) response in a 79-day greenhouse pot …

Dna Aptamer‑Based Rolling Circle Amplification Product As A Novel Immunological Adjuvant, Adil Sabr Al-Ogaili, Rohana Liyanage, Jack O. Lay Jr., Tieshan Jiang, Christine N. Vuong, Shilpi Agrawal, Thallapuranam Krishnaswamy Suresh Kumar, Luc R. Berghman, Billy M. Hargis, Young Min Kwon

Chemistry & Biochemistry Faculty Publications and Presentations

Several agonists to CD40 have shown to induce acquired immune responses. Here, we developed and evaluated the rolling circle amplification (RCA) products that are based on anti-CD40 DNA aptamers as a novel vaccine adjuvant. First, we developed DNA aptamers with specific binding affinity to chicken CD40 extra domain (chCD40ED). Next, we prepared the RCA products that consist of these aptamers to increase the spanning space and overall binding affinity to chCD40ED. Using 8 DNA aptamer candidates, 4 aptamer-based RCA products (aptamer RCAs) were generated, each consisting of two distinct aptamers. We demonstrated that all 4 aptamer RCAs significantly induced the …

P450 Cyp17a1 Variant With A Disordered Proton Shuttle Assembly Retains Peroxo-Mediated Lyase Efficiency, Yilin Liu, Ilia G. Denisov, Yelena V. Grinkova, Stephen G. Silgar, James R. Kincaid

Chemistry Faculty Research and Publications

Human cytochrome P450 CYP17A1 first catalyzes hydroxylation at the C17 position of either pregnenolone (PREG) or progesterone (PROG), and a subsequent C₁₇−C₂₀ bond scission to produce dehydroepiandrosterone (DHEA) or androstenedione (AD). In the T306A mutant, replacement of the Threonine 306 alcohol functionality, essential for efficient proton delivery in the hydroxylase reaction, has only a small effect on the lyase activity. In this work, resonance Raman spectroscopy is employed to provide crucial structural insight, confirming that this mutant, with its disordered proton shuttle, fails to generate essential hydroxylase pathway intermediates, accounting for the loss in hydroxylase efficiency. Significantly, …

Polymer-Based Capacitive Gas Sensor For Machine Olfaction, Mohamed Fathy Hassan

Theses and Dissertations

Transferring human abilities and knowledge to machines has been the focus of decades of work by scientists and engineers. With the progress in computation power and algorithms such as artificial neural networks, machines have surpassed humans in complicated games like chess and the Chinese game Go. Some senses can be mimicked including touch, with pressure sensors, hearing, with microphones, and vision with charged couple device (CCD)imaging chips. Yet, relatively little progress has been made with the senses of smell and taste. Machine olfaction, the ability to detect and quantify vapors in the environment, poses a range of challenges, which if …

Triggerable, Targetable, And Trackable Flavonol-Based Carbon Monoxide-Releasing Molecules, Livia S. Lazarus

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Long known as a toxic gas, carbon monoxide (CO) has been recently redefined as a health beneficial molecule produced endogenously in humans. The biological activity of CO has been extensively examined in inflammatory conditions, vasoprotection, anti-apoptotic and anticancer studies, although the mechanisms of action are still not well defined. Because CO is a gaseous molecule, a straightforward administration would be inhalation. However, this delivery method is limited to use in hospital settings under professional supervision. For improved control over the amount and location of CO delivery, metal-free and light-triggered carbon monoxide-releasing molecules are of particular current interest. Our lab is …

Synthesis And Characterization Of Carbohydrate Based Molecular Gelators And Macrocycles Through Cycloaddition Reactions, Dan Wang

Chemistry & Biochemistry Theses & Dissertations

Carbohydrate based low molecular weight gelators (LMWGs) are biocompatible and have many potential applications. They have been used for drug delivery, environmental clean-up, and for reaction catalysis. In recent years, copper catalyzed azide alkyne cycloaddition reactions (CuAACs) also termed “Click reactions” have shown great applications in the synthesis of various glycoconjugates and carbohydrate derivatives.

In this research, three diverse classes of glycoconjugates (I, II, III) have been designed and synthesized. The first class of compounds (I) in Chapter 2 are D-glucosamine based amide and triazole derivatives with different spacers between the amide and triazole (n=2-5) function groups. These compounds were …

Synthesis, Characterization, Spectroscopic, And Mesomorphic Studies Of New Schiff Base Ligands And Titanium, Cobalt, Nickel And Copper Metal Centers, Raj K. Gurung

Chemistry & Biochemistry Theses & Dissertations

Transition metal complexes with Schiff base ligands offer a wide application in the field of development of catalysis and material. The straightforward synthesis allowed the structural modification and helped to optimize in various application of such complexes. Titanium-containing complexes have been reported to be important for their catalytic and material applications through the coordination of a tetradentate Schiff base ligand, viz. N, N’-ethylene bis(salicylideneiminate) dianion (salen). Studies reporting the characterization of achiral titanium(IV) salen complexes are scarce due to their intricate nature. Such complexes would be comparatively less expensive and easier to prepare synthetically and thus could represent an …

Advances In The Understanding Of Sourcing And Fate Of Pyrogenic Organic Matter In The Environment, Aleksandar Ivaylov Goranov

Chemistry & Biochemistry Theses & Dissertations

With higher occurrences of forest fires worldwide, there has been an increase in scientific interest surrounding the chemistry of pyrogenic organic matter (pyOM). The main structural components of pyOM, the condensed aromatic compounds (ConAC), exhibit intriguing physico-chemical properties and have been one of the main focuses of biogeochemical research. The overwhelmingly large number of scientific articles regarding pyOM and ConAC are guided by the assumption that ConAC in the environment are exclusively of pyrogenic origin, even though some recent studies have suggested that some of these ConAC could also be derived from non-pyrogenic radical-driven processes. To evaluate this controversial proposition, …

Synthesis, Characterization, And Kinetics Studies Of New Cobalt Complexes For The Production Of H2 In Acidic Media, Michael John Celestine

Chemistry & Biochemistry Theses & Dissertations

The kinetics and mechanism of the oxidation of [Co(dmgBF₂)₂(OH₂)₂] (where dmgBF₂ = difluoroboryldimethylglyoximato) by sodium hypochlorite (NaOCl), sodium bromate (NaBrO₃), and bromine (Br₂₎ was investigated by stopped-flow spectrophotometry at 450 nm over a wide temperature range. The pK_a1 value for [Co(dmgBF₂)₂(OH₂)₂] was calculated as 5.27 ± 0.14 at I = 0.60 (NaCl). From the variation in pH studies, the activation parameters were derived from the proposed mechanisms for NaOCl, ΔH_1*, ΔH_2*, ΔS_1*, and …

Aryne-Guided C-H Functionalization Of Benzenoid Rings Using Diaryliodonium Salts, Aleksandra Nilova

Dissertations and Theses

The benzenoid core is a frequent and irreplaceable component of biologically active molecules. Structure function relationship of these compounds has been broadly analyzed and presented in numerous literature reports. Herein, we augmented existing knowledge by a broad analysis of the benzenoid substitution patterns in small molecule active pharmaceutical ingredients approved by the FDA. Our findings reveal a strong correlation that the most represented substitution patterns are those achieved via S_EAr. Despite the rapid development of methods to functionalize benzenoid rings, the lack of synthetic methodologies to access sterically and electronically unfavorable positions is highlighted. We sought to establish …

Chloramination Of Iopamidol- And Bromide-Spiked Waters Containing Natural Organic Matter, Nana Osei B Ackerson, Hannah K. Liberatore, Susan D. Richardson, Micheal J. Plewa, Thomas A. Ternes, Stephen E. Duirk

Faculty Publications

Iopamidol (an iodinated X-ray contrast medium) and bromide are precursors in the formation of halogenated disinfection byproducts (DBPs). The interactions of these precursors are vital to elucidate the formation of halogenated DBPs during chloramination. This work investigated the formation of total organic halogen and select individual DBPs in two laboratory-chloraminated source waters containing iopamidol and bromide. Experiments were carried out in batch reactors containing Barberton source water (BSW) and Cleveland BSW (CSW), spiked with iopamidol (5 mu M), bromide (15 mu M), and 100 mu M monochloramine. Total organic iodine concentrations were approximately equal regardless of source water since they …

Biosynthetic Gene Clusters, Microbiomes, And Secondary Metabolites In Cold Water Marine Organisms, Nicole Elizabeth Avalon

USF Tampa Graduate Theses and Dissertations

Microorganisms and invertebrate animals from cold water marine environments, such as in Antarctica and in Ireland’s deep sea, are a rich source of secondary metabolites. In this dissertation, research was centered around secondary metabolism and natural product biosynthesis. The projects include the delineation of biosynthetic gene clusters hypothesized to be responsible for the biosynthesis of the palmerolides, stratification of the microbiome of the Antarctic ascidian Synoicum adareanum, genomic and peptidomic analysis of a host-associated Antarctic Pseudovibrio sp., and isolation and characterization of secondary metabolites from the Irish deep-sea coral Drifa sp.

Palmerolide A, the principle secondary metabolite associated with S. …

Unspecified Verticality Of Franck-Condon Transitions, Absorption And Emission Spectra Of Cyanine Dyes, And A Classically Inspired Approximation, Joseph D. Alia, Joseph A. Flack

Chemistry Publications

The computed vertical energy, Ev,a/f, from the equilibrium geometry of the initial electronic state is frequently considered as representative of the experimental excitation/emission energy, Eabs/fl = hc/λmax. Application of the quantum mechanical version of the Franck–Condon principle does not involve precise specification of nuclear positions before, after, or during an electronic transition. Moreover, the duration of an electronic transition is not experimentally accessible in spectra with resolved vibrational structure. It is shown that computed vibronic spectra based on TDDFT methods and application of quantum mechanical FC analysis predict Eabs = hc/λmax …

Multi-Institution Research And Education Collaboration Identifies New Antimicrobial Compounds, Amelia A. Fuller, Amy B. Dounay, Douglas Schirch, Daniel G. Rivera, Karl A. Hansford, Alysha G. Elliott, Johannes Zuegg, Matthew A. Cooper, Mark A. T. Blaskovich, Jacob R. Hitchens, Sarah Burris-Hiday, Kristiana Tenorio, Yanira Mendez, J. Geno Samaritoni, Martin J. O’Donnell, William L. Scott

Chemistry and Biochemistry

New antibiotics are urgently needed to address increasing rates of multidrug resistant infections. Seventy-six diversely functionalized compounds, comprising five structural scaffolds, were synthesized and tested for their ability to inhibit microbial growth. Twenty-six compounds showed activity in the primary phenotypic screen at the Community for Open Antimicrobial Drug Discovery (CO-ADD). Follow-up testing of active molecules confirmed that two unnatural dipeptides inhibit the growth of Cryptococcus neoformans with a minimum inhibitory concentration (MIC) ≤ 8 μg/mL. Syntheses were carried out by undergraduate students at five schools implementing Distributed Drug Discovery (D3) programs. This report showcases that a collaborative research and educational …

Study On Cation Exchange Of A Lead Coordination Polymer Targeting Dynamic Mixed Cation Doped And Mixed-Valent Coordination Polymers, Hamisu Aliyu Mohammed

Student Works (2020-2029)

Solid solution in Metal-Organic Coordination Polymers (MOCPs) is an emerging synthetic pathway for modifying chemical compositions and has been expansively investigated. It has been demonstrated to be an important tool for engineering novel functional materials that otherwise have not been synthesized via the conventional technique. Although stable solid material with variable functionalities and intriguing structural motifs could be engineered by judicious selection of multivariate metal centers and multifunctional ligands. However, solid solution featuring mixed valence in MOCP is rare. Motivated by the ability of Pb2+ to adopt range of coordination numbers (CN) and chemical environments (CE), in addition to its …

Cationic Boron Formazanate Dyes, Benjamin D. Katzman, Paul D. Boyle, Viktor N. Staroverov, Joe Gilroy, Ryan R. Maar

Chemistry Publications

Incorporation of cationic boron atoms into molecular frameworks is an established strategy for creating chemical species with unusual bonding and reactivity but is rarely thought of as a way of enhancing molecular optoelectronic properties. Using boron formazanate dyes as examples, we demonstrate that the wavelengths, intensities, and type of the first electronic transitions in BN heterocycles can be modulated by varying the charge, coordination number, and supporting ligands at the cationic boron atom. UV‐vis absorption spectroscopy measurements and density‐functional (DFT) calculations show that these modulations are caused by changes in the geometry and extent of π‐conjugation of the boron formazanate …

One-Step Synthesis Of Soybean Oil-Based Polyol For Highly Flame-Retardant Rigid Polyurethane Foams, Tenzin Ingsel

Electronic Theses & Dissertations

The usage of petro-chemical based sources in polyurethane has raised environmental concerns in recent years. Bio-based polyurethanes are attractive alternatives for these conventional petrochemical-based polyurethanes. In this work, a soybean oil-based polyol was synthesized via thiol-ene reaction. Chromatography, wet chemistry methods, and spectroscopic evaluations were carried out to characterize the synthesized polyol. The polyol obtained was then used to produce flame-retardant rigid polyurethane foams with three different organophosphorus flame-retardants: dimethyl methyl phosphonate (DMMP), triethyl phosphate (TEP), and triphenyl phosphate (TPP). Incorporating flame-retardants in polyurethane foams provide them resistance to ignition where these foams are originally highly combustible. Physico-mechanical and flammability …

Editorial: Carbon- And Inorganic-Based Nanostructures For Energy Applications, Federico Cesano, M. Jasim Uddin, Yuanbing Mao, Muhammad N. Huda

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

No abstract provided.

Atom Trapping And Its Role On The Nucleation & Growth Of Platinum Nanoparticles, Deepak Kunwar

Chemistry and Chemical Biology ETDs

Diesel oxidation catalysts deactivate due to Pt sintering, a major problem in automotive industries. To make sure they operate effectively throughout the lifetime of the vehicle, automotive industries are putting an excessive amount of Pt. There is a need to develop a catalyst that serves long term performance with minimal use of Pt. Jones et al^.1 demonstrated that ceria traps Pt atoms. His work generated some logical and valid questions such as what is the mechanism for the formation of anomalously large Pt particles? What is the upper limit of Pt metal loading in the form of single atoms …

Deep-Ultraviolet Laser Ablation For Biomolecular Analysis, Oluwaremilekun Omowunmi Lawal

LSU Doctoral Dissertations

New sampling and ionization techniques were developed using a deep-ultraviolet (DUV) laser at 193 nm wavelength for analysis of large biomolecules. A micrometer spatial resolution DUV laser ablation and capture system was constructed to sample tissue biomolecules. The spot size measurements of the focused beam showed that subcellular spots with ca. 2 μm diameter can be readily achieved with this wavelength. To demonstrate the extraction of tissue biomolecules with the DUV laser, regions of tissue sections were ablated and captured for offline proteomic and genomic analysis. The proteomic studies revealed that the tissue proteins were ejected without fragmentation and that …

Structure And Dynamics Of Phospholipid Vesicles And The Dependence On Nanoscale Interactions With Molecules Of Varying Complexity, Lakshapathy Widanelage Judith Upeka De Mel

LSU Doctoral Dissertations

In this dissertation, molecular interactions and changes imposed by nano-scale structures on phospholipid vesicles were investigated. 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) large unilamellar vesicles (LUVs) were used as the model system. Understanding changes of the bilayer structure, interfacial properties, lipid dynamics, and self-assembly, allows bridging relationships between biological cell membrane structure and dynamics to cellular functionalities. For example, membrane curvature changes are linked to membrane protein functions, although the exact mechanisms of control are not yet understood. Moreover, the knowledge gained from vesicle models allows exploring novel strategies for drug delivery applications. To achieve this, DOPC LUVs were synthesized and characterized by a …

Computational Investigations Of Battery Electrolytes, Ke Li

LSU Doctoral Dissertations

In this dissertation, the structure and dynamics of battery electrolytes were investigated using atomistic molecular dynamics (MD) simulations. Battery electrolytes play a key role in transporting ions between the cathode and anode. The chemical stability and ionic conductivity of electrolytes influence battery performance. In order to design better electrolytes, one needs an understanding of the relationship between electrolyte structure, dynamics, and bulk properties. To bridge the gap between the macroscopic phenomenon and the hidden molecular physics, in the first project we focused on probing an ether-based electrolyte, chosen for its relevance in sodium-based batteries. Through studying the impact of concentration …

Natalia Shustova Answers Questions About 15 Years Of Research On Covalent Organic Frameworks, Natalia B. Shustova Prof. Dr.

Faculty Publications

No abstract provided.