Chemistry Commons^™

Laser Spectroscopy Investigations Of Jet-Cooled Metal-Containing Free Radicals., Anam Chandra Paul

Electronic Theses and Dissertations

Metal-containing free radicals are important intermediates in metal-surface reactions and the interactions between metals and organic molecules. Among metal-containing free radicals, monovalent derivatives of alkaline earth metals have been extensively investigated by using spectroscopic techniques in a gas phase, mainly in Broida ovens or under supersonic-jet-cooled conditions. In the present study, the results of performed spectroscopic investigations of both metal-containing monoalkoxides (CaOR) and metal oxides (MO) radicals have been reported. Laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the electronic transition of the calcium CaOR radicals have been obtained under jet-cooled conditions. Complete active space self-consistent field (CASSCF) and …

Gc×Gc-Ms And Parallel 2dlc-Ms Based Untargeted Metabolomics., Md Aminul Islam Prodhan

Electronic Theses and Dissertations

Untargeted metabolomics aims to analyze as many metabolites as possible in a biological system. Due to the vast complexity of the metabolome, bioanalytical platforms have been developed for untargeted metabolomics. While comprehensive two-dimensional gas chromatography mass spectrometry (GC×GC-MS) has been used in different scientific fields, its use in untargeted metabolomics is limited due to several challenges, such as complicated data analysis and limited accuracy of metabolite identification. Two-dimensional liquid chromatography mass spectrometry (2DLC-MS) has also been employed in untargeted metabolomics, but with limited metabolite coverage. This dissertation describes the efforts in developing new data analysis algorithms to improve the accuracy …

Synthesis And Study Of Hydroxytyrosol Derivatives, Ebenezer Ametsetor

Electronic Theses and Dissertations

Hydroxytyrosol is one of the most powerful known antioxidants. It is a naturally occurring polyphenol, most commonly produced in olive trees, (Olea europaea). The remarkable antioxidant and pharmacological properties of hydroxytyrosol has made it an outstanding compound in the polyphenol family and of great interest to many researchers. Hydroxytyrosol can scavenge free radicals produced during cellular oxidative stress and helps to protect the integrity of cells in living systems. Despite its numerous biological and pharmacological uses, it is found in very low concentration in olive oil, this limits its availability for biomedical applications. This work reports a novel and effective …

Photocatalytic Degradation Of Simazine Under Visible Light Using Zinc Oxide/Molybdenum Disulfide Heterostructures, Alexandria Castillo

Theses and Dissertations

The photocatalytic degradation of simazine under visible light by using ZnO/MoS2 heterostructures was investigated. Reaction parameters studied to optimize simazine degradation included pH, loading mass of the photocatalyst, and percentage of MoS2 in the heterostructure. pH 2 was the optimal environment for the degradation reaction of all catalysts. A loading mass of 20 mg for each of the ZnO/MoS2 photocatalysts was determined to be the most effective for in the degradation process. The degradation reactions were observed to follow 2nd order kinetics for all photocatalysts at all temperatures. Band gap studies confirmed a lower energy than that of pure ZnO …

Oxygen Deficient Perovskites: Effect Of Structure On Electrical Conductivity, Magnetism And Electrocatalytic Activity., Ram Krishna Hona

Electronic Theses and Dissertations

The present thesis deals with the synthesis and study of the physico-chemical properties of perovskite based oxide materials. Several novel oxygen deficient perovskites (ODP) have been synthesized by conventional solid state synthesis method. The novel compounds are CaSrFe₂O_6-δ, CaSrFeCoO_6-δ, Ca₂Fe_1.5Ga_0.5O₅, CaSrFeGaO₅ and BaSrFe₂O₅. Their magnetic, charge transport and electrocatalytic properties have been studied. Structural effect on electrical conductivity, magnetic and electrocatalytic properties have been studied in some series of ODPs. CaSrFe₂O_6-δ, CaSrFeCoO_6-δ, Ca₂Fe …

Laser Spectroscopic Investigations Of Organic Alkoxy And Peroxy Radicals., Md Asmaul Reza

Electronic Theses and Dissertations

Understanding the mechanism of combustion reactions is key for advancing internal combustion engine design, improving the efficiency of ignition chemical reactions, and reducing pollutant formation. In order to model the extremely complicated chemical kinetics of combustion processes, it is critical to detect and identify transient reactive chemical intermediates, particularly free radicals. Hence, it needs to be fully understood the gas-phase chemistry of organic compounds in the lower atmosphere. Over the past fifty years, parallel advancement in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role of organic compounds in the atmosphere. Combustion chemistry …

Effects Of The Dihydrouracil Lesion On Dna Using 1h/31p 1d And 2d Solution Nmr, Benjamin M. Boyd

Graduate Theses/Dissertations

The effects of the dihydrouracil lesion in DNA were studied using two dimensional NMR spectroscopy. The sequence used was based off of the Drew-Dickerson Dodecamer, with the cytosine in the three position replaced by a dihydrouracil. All of the nonexchangeable proton chemical shifts, with the exception of the H2, H5’, and H5’’, of the lesioned DNA were identified using NOESY spectra and then compared to the chemical shift values of the Drew Dickerson Dodecamer. The largest differences in chemical shifts were observed in the nucleotides neighboring the lesion, both within the strand and on the opposite strand. The imino exchangeable …

Ultrafast Relaxation Dynamics In Graphene Oxide-Dye And Perovskites Nanocomposites, Abubkr A. Arzaq Abuhagr

Dissertations

Novel materials such as graphene oxide (GO), reduced graphene oxide (RGO), and Perovskites nanocomposites nanosheets have shown interesting electrical and optical properties. These materials have shown prominence in research regarding optical sensing applications. The interaction of different fluorescent molecules like dye molecules with GO, and RGO have been studied recently to develop novel optical sensors, photo-catalysts, and light-harvesting agents. In this study, we have monitored the excited state interactions of dyes covalently attached to GO and RGO nanosheets. Three amine derivatives of anthracene, pyrene, and coumarin were covalently bound to different systems via amide bonds and diazotization. Characterization of different …

Smart Sensors With Dual Modes Of Signal Transduction For Monitoring Molecules Pertinent To Health And The Environment, Jared T. Wabeke

Dissertations

The dissertation focuses on the design and synthesis of smart materials for the detection of molecules pertinent to environmental protection and healthcare. The use of computational simulations is pivotal toward advancing molecular design for targeted applications. Research was conducted to investigate the use of simulations to develop novel sensors with dual modes of signal transduction. The molecular properties were determined using computational modelling, and then used to elucidate the binding mechanism of the corresponding sensor complexes. Several molecules were produced that respond to important organic analytes, such as glucose and fenthion, an organophosphorus pesticide. Glucose is an exceedingly important biological …

Probing Of Carbohydrate-Protein Interactions Using Galactonoamidine Inhibitors, Jessica B. Pickens

Graduate Theses and Dissertations

Glycoside hydrolases are ubiquitous and one of the most catalytically proficient enzymes known, and thus understanding their mechanisms are crucial. Most research has focused on the interaction of the glycon of substrates and their inhibitors within the active site of glycoside hydrolases. The inhibitors employed to probe these interactions generally had small aglycons (i.e. a hydrogen atom, amidines, small aliphatic groups, or benzyl groups). Here, the interactions of the aglycon with glycoside hydrolases are examined by probing the active sites with a library of 25 galactonoamidines. The studies described in this dissertation aim to increase the understanding of stabilization of …

Aglycon Modifications Of Ipomoeassin F: Synthetic Route Development And Analog Synthesis To Enable Further Sar Studies, Eric Barber

Graduate Theses and Dissertations

The ipomoeassin family of resin glycosides were discovered to have a high potency against numerous cancer cell line, with ipomoeassin F being the most potent among the family of natural products. Interestingly, one of the few differences between ipomoeassin F and the other compounds is the length of the fatty-acid derived aglycon. As the mechanism of action for this family of resin glycosides is unknown and didn’t have any significant COMPARE correlation with the recorded anticancer agents in the National Cancer Institute (NCI), further SAR studies are needed. Drawing on the differences between ipomoeassin F and the other ipomoeassins, it …

Structure Elucidation Of A Pyrrolobenzodiazepine Alkaloid And A Biologically Active Polyketide Produced By Rhodococcus Sp. Mtm3w5.2 Via Two-Dimensional Nmr Spectroscopy, Garrett Johnson

Electronic Theses and Dissertations

As the battle against ever-increasing drug resistence bacteria rages on, novel and sometimes more complex natural products can be used to combat this. In this study, two-dimensional NMR techniques were utilized to collect a complete spectral data set for two natural products. The first structure, a synthesized Pyrrolobenzodiazepine alkaloid natural product was confirmed through these methods. The second, a strain of Rhodococcus, MTM3W5.2, produces a novel antibacterial molecule in broth cultures and the active compound was fractionated using a Sephedex LH-20 column. Chromatographic purification yielded a pure sample at 58.90 minutes, RT.58. HRMS data deduced an exact mass of …

Preparation Of Folic Acid-Carbon Dots-Doxorubicin Nanoparticles As Targeting Tumor Theranostics, Samson Dada

Electronic Theses and Dissertations

Carbon dots (CDs) have attracted much attention as an excellent gene/drug delivery and biological imaging agent for early cancer theranostics. In this study, we prepared two series of nanoparticles (NPs), which are composed of (CDs) with a targeting agent, folic acid (FA), and a chemotherapeutic agent Doxorubicin (Dox). All the NPs and their intermediates were characterized using ultraviolet-visible spectroscopy (UV-vis), fluorescence spectroscopy, and Fourier transform-infrared spectroscopy (FT-IR). The drug loading capacity (DLC) and drug loading efficiency (DLE) of two series of FA-CDs-Dox were assessed using UV-vis absorption spectroscopy at the wavelength of 485 nm. Both showed good DLE and DLC …

Development Of Forward Osmosis Based Separations: A Novel Approach In Membrane Technology, Yu-Hsuan Chiao

Graduate Theses and Dissertations

Tackling the worldwide severe water shortage, the membrane technology is considered to be the most efficient approach and hence, used widely as a cost-effective sustainable solution. “Forward osmosis (FO)” has been the major attention in recent time. FO uses osmotic pressure as the driving force to draw the water passing the membrane and achieve the desired separation performance. In general, it is considered to be a process with tremendous potential to resolve the present-day water shortage with extremely low energy consumption. However, the challenges of membrane and draw solution regeneration associated with FO processes must be conquered prior to their …

Rotational Tuning Of Transmembrane Helix Properties Based On The Precise Placements Of Aromatic And Charged Residues, Matthew J. Mckay

Graduate Theses and Dissertations

Designed model transmembrane peptides and oriented 2H and 15N solid-state nuclear magnetic resonance (NMR) spectroscopy were used to analyze how simple sequence modifications can influence peptide structure, behavior and dynamics as well as for determining the pKa of glutamic acid at the membrane interface. The GW5,19ALP23 (acetyl-GGALW(LA)6LWLAGA-amide) peptide framework adopts a well-defined tilted orientation in lipid bilayers (DLPC, DMPC and DOPC) and undergoes low amounts of dynamic motion. The sequence was initially modified by moving the Trp residues outwards to positions 4 and 20. This new sequence GW4,20ALP23 (acetyl-GGAW(AL)7AWAGA-amide) displays high amounts of signal averaging of NMR observables caused by …

Reactivity Of Photogenerated Amine Radical Cations, Qile Wang

Graduate Theses and Dissertations

Recently photoredox catalysis has emerged as a powerful tool in organic synthesis led by Professor McMillan, Stephenson, Yoon. Upon absorption of visible light, photocatalyst can be excited to its singlet state followed by intersystem crossing to form a long lived excited triplet state. While amine serves as electron donor, single electron transfer (SET) can happen between excited triplet photocatalyst and nitrogen atom on amine to give a reduced photocatalyst and amine radical cation.

Cyclopropylamines or cyclobutylamines can be oxidized by excited photocatalyst to generate amine radical cations and due to the ring strain, subsequent C-C bond cleavages can lead to …

Understanding And Controlling Lithium Microstructure During Electroplating For Energy Applications, Yang Tian

Graduate Theses and Dissertations

Lithium-ion batteries are reaching the specific theoretical capacity limit, while lithium metal batteries are regarded as the ideal energy storage system for the next generation “beyond lithium-ion” battery systems. The lithium metal anode is considered as the “Holy grail” of anodes due to its relatively low electrochemical potential (-3.04 V vs SHE) and high theoretical capacity (3860 mAh g-1). However, the application of lithium metal anodes is hindered because of significant reaction between metallic lithium and electrolytes, as well as uneven electro-plating, which leads to dendrite formation, causing safety problems.

The kinetic parameters of Li ions such as diffusion coefficient …

Cost-Effective Synthesis, Bioactivity And Cellular Uptake Study Of Aminoglycosides With Antimicrobial And Connexin Hemichannel Inhibitory Activity, Yagya P. Subedi

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Amphiphilic kanamycin is one of the promising class of compounds for the treatment of fungal infections in plants and animal. Factor that lead to the restricting of compounds for commercialization includes, the higher cost of production and poor stability of the compound. However, the new lead, identified from the synthesis and biological testing, can be synthesized on a large scale with a cost comparable to commercial antifungals. The newly reported lead is stable at the acidic and basic conditions. Additionally, this compound has an excellent activity towards Candida auris, a multidrug-resistant superbug.

Heart disease is the leading cause of death …

Synthesis, Characterization, And Drug Delivery Applications Of Carbohydrate Based Low Molecular Weight Gelators, Kristen Elizabeth Bashaw

Chemistry & Biochemistry Theses & Dissertations

The main aim of the research focuses on the study of self-assembly and gelation by several classes of simple sugar derivatives and the potential applications of them as drug delivery vehicles. Since carbohydrates are naturally abundant renewable resources and are therefore readily available and many of them are inexpensive compared to other raw materials. They are also biocompatible which makes them suitable for a wide variety of applications. Combining the use of carbohydrates with low molecular weight gelators (LMWGs) we can introduce a new class of soft materials that are able to self-assemble into spheres, fibers, sheets, and micelles in …

Isotopic Characterization Of Nitrogen Oxides (NoX), Nitrous Acid (Hono), And Nitrate (PNo3-) From Laboratory Biomass Burning During Firex, Jiajue Chai, David J. Miller, Eric Scheuer, Jack Dibb, Vanessa Selimovic, Robert Yokelson, Kyle K. Zarzana, Steven Brown, Abigail R. Koss, Carsten Warneke, Meredith Hastings

Chemistry and Biochemistry Faculty Publications

New techniques have recently been developed and applied to capture reactive nitrogen species, including nitrogen oxides (NOx D NOCNO2), nitrous acid (HONO), nitric acid (HNO3), and particulate nitrate (pNO3 ), for accurate measurement of their isotopic composition. Here, we report – for the first time – the isotopic composition of HONO from biomass burning (BB) emissions collected during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) at the Missoula Fire Science Laboratory in the fall of 2016. We used our newly developed annular denuder system (ADS), which was verified to completely capture HONO associated …

Gaseous, Pm2.5 Mass, And Speciated Emission Factors From Laboratory Chamber Peat Combustion, John G. Watson, Junji Cao, Lung-Wen Antony Chen, Qiyuan Wang, Jie Tian, Xiaoliang Wang, Steven Gronstal, Steven Sai Hang Ho, Adam C. Watts, Judith C. Chow

School of Public Health Faculty Research

Peat fuels representing four biomes of boreal (western Russia and Siberia), temperate (northern Alaska, USA), subtropical (northern and southern Florida, USA), and tropical (Borneo, Malaysia) regions were burned in a laboratory chamber to determine gas and particle emission factors (EFs). Tests with 25 % fuel moisture were conducted with predominant smoldering combustion conditions (average modified combustion efficiency (MCE) =0.82+/-0.08). Average fuel-based EFCO2 (carbon dioxide) are highest (1400 +/- 38 g kg(-1)) and lowest (1073 +/- 63 g kg(-1)) for the Alaskan and Russian peats, respectively. EFCO (carbon monoxide) and EFCH4 (methane) are similar to 12 %15 % and similar to …

Conformational Polymorphism In Organic Crystals: Structural And Functional Aspects - A Review, Bidisha Sengupta, Pradeep K. Sengupta, Romans Grant1, Matthew Beasley1, Benjamin Mason1, Tanesha Love1, Larissa Barroso9, Mariela Alvarado9, M S. Zaman

Faculty Publications

Polymorphism in organic crystals involves the formation of isomeric molecular identities. It is dependent on the structural arrangement due to inter-atomic interactions, as well as external stimuli, which include temperature, visible and UV radiation. Conformational polymorphism of organic crystalline molecules is often the result of isomerism due to the twisting and turning of angular bonds. The arrangement of the atoms supports different types of bonding mechanisms (which include hydrogen bonding) within the same compound. This, in turn, results in the formation of cis/trans configurational isomers or a proton transfer species (tautomer), having different functional properties. The conformers support the flexibility …

Synthesis Of Chromium (Iii) Complexes With Phenanthroline Fused Imidazole Ligands, Wasilat Adeoluwa

3 Minute Thesis Competition

No abstract provided.

Effect Of Ozone Layer Depletion, Omotayo Jacob

3 Minute Thesis Competition

No abstract provided.

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

Chemical Tools And Treatments For Neurological Disorders And Infectious Diseases, Andrea Lemus

USF Tampa Graduate Theses and Dissertations

Neurological disorders have multiple etiologies such as genetics and age. Stress related disorders are becoming more common and diagnosed more often. Mental health disorders are no longer being treated as purely psychological. Mechanisms into the underlying factors of these disorders continue to bring this area to new frontiers. Chapter 2 of this dissertation focuses on the efforts made to prove the association of the protein FKBP51 to the stress response. We synthesized and used a molecular tool to discover and prove these interactions.

The study of neurodegenerative diseases is of continued importance as the world reaches record numbers of an …

Antarctic Deep Sea Coral And Tropical Fungal Endophyte: Novel Chemistry For Drug Discovery, Anne-Claire D. Limon

USF Tampa Graduate Theses and Dissertations

Considered the pulse controlling the biological interactions and contributing to the ecological survival of organisms, natural products have intrigued, challenged, and stimulated the scientific and non-scientific minds for millennia. Drug resistance and the lack of suitable potent drugs against neglected tropical diseases further motivate the biological activity assessment of these secondary metabolites, when possible.

This thesis describes the chemical investigation of two marine organisms and the elucidation of eight novel structures.

The study of a deep sea Antarctic coral unveils six novel terpenoid structures from three different molecular classes: sesquiterpenoid alcyopterosins, a triterpene steroid, and three prostaglandins. While mass availability …

Assessing The Efficacy Of Virtual Experiments In The General Chemistry Laboratory, Cory Jerome Hensen

Dissertations and Theses

As more students enroll in chemistry courses, institutions are faced with increasing costs and limited laboratory space to keep up with the demand. One solution some institutions have turned to is the incorporation of virtual experiments into the curriculum, as this can lower costs and increase the availability of laboratory space. Some institutions have offered sections that complete all of their experiments in a virtual environment, others have offered sections that alternate between a traditional hands-on experiment and a virtual experiment, and some institutions have replaced only select experiments throughout the curriculum with a virtual experiment. To begin to be …

Facile One-Pot Synthesis Of Nico₂Se₄-Rgo On Ni Foam For High Performance Hybrid Supercapacitors, Bahareh Golrokh Amin, Jahangir Masud, Manashi Nath

Chemistry Faculty Research & Creative Works

A facile, innovative synthesis for the fabrication of NiCo₂Se₄-rGO on a Ni foam nanocomposite via a simple hydrothermal reaction is proposed. The as-prepared NiCo₂Se₄-rGO@Ni foam electrode was tested through pxrd, TEM, SEM, and EDS to characterize the morphology and the purity of the material. The bimetallic electrode exhibited outstanding electrochemical performance with a high specific capacitance of 2038.55 F g^-1 at 1 A g^-1. NiCo₂Se₄-rGO@Ni foam exhibits an extensive cycling stability after 1000 cycles by retaining 90% of its initial capacity. A superior energy density …

Development Of Fertilizer Coatings From Polyglyoxylate-Polyester Blends Responsive To Root-Driven Ph Change., Spencer M Heuchan, Bo Fan, Jessica J Kowalski, Elizabeth R Gillies, Hugh A L Henry

Chemistry Publications

Many current controlled-release fertilizers (CRFs) are coated with nonbiodegradable polymers that can contribute to microplastic pollution. Here, coatings of self-immolative poly(ethyl glyoxylate) (PEtG) capped with a carbamate and blended with polycaprolactone (PCL) or poly(l-lactic acid) (PLA) were evaluated. They were designed to depolymerize and release fertilizers in the vicinity of plant roots, where the pH is lower than that in the surrounding environment. PEtG/PCL coatings exhibited significant temperature and pH effects, requiring 18 days at pH 5 and 30 °C, compared to 77 days at pH 7 and 22 °C, to reach 15% mass loss. Plant roots were also effective …