Chemistry Commons^™

Biomimetic Synthesis Of Palladium Nanoparticles For Catalytic Application, Emily A. Groover

College of Graduate Studies: Theses & Dissertations

The synthesis of palladium nanoparticles (Pd NPs) using materials-directed peptides is a novel, nontoxic approach which exerts a high level of control over the particle size and shape. This biomimetic technique is environmentally benign, featuring nonhazardous ligands and ambient conditions. Nanoparticles are extremely reactive catalysts, boasting a large surface-to-volume ratio when compared to their bulk counterparts. The rational design of these nanoparticles using peptides has been very successful in aqueous environments, but no research has been done to apply it in organic systems. As such, the biomimetic synthesis of Pd NPs in an organic system is here investigated, with ethanol …

Tandem Addition/Fragmentation Reactions Of Vinylogous Acyl Sulfonates, Kristen S. Nerbecki

Graduate Theses, Dissertations, and Problem Reports (ETD)

Fragmentation methodology has been used in organic synthesis to produce complex organic compounds. This work is focused on fragmentation reactions leading to the subsequent construction of neopentylene-fused carbocycles, which are found in several important natural products and are difficult to prepare. These are produced by utilizing an optimized fragmentation methodology from the Dudley group. The methodologies build starting materials called nonaflates and triflates with a gem-dimethyl substituent that is seen in many natural products. Nonaflates and triflates are similar in structure, but nonaflates pose benefits that are an advantage over triflates, like cost effective synthesis and more stable compounds. A …

Capillary Electrophoresis: Method Development And Application In Biomolecule Analysis, Lindsay Marie Veltri

Graduate Theses, Dissertations, and Problem Reports (ETD)

Abstract

Capillary Electrophoresis: Method Development and Application in Biomolecule Analysis

Lindsay Veltri

Biomolecule analysis is essential in disease diagnostics and the development of therapeutic agents. There is a vast array of methods available for biomolecule analysis, however, capillary electrophoresis is well-suited due to minimal sample consumption (~nanoliters of solution) and fast analysis times. In this report, capillary electrophoresis was used to analyze glycosylation of therapeutic proteins. Additionally, a capillary electrophoresis-mass spectrometry method is reported for the analysis of proteins.

Post-translation protein modifications like glycosylation, play an important in protein structure and function. Modifications of protein glycosylation can lead to improved …

Novel Modes Of Synchronization And Extreme Events In Coupled Chemical Oscillators, David Allen Mersing

Graduate Theses, Dissertations, and Problem Reports (ETD)

We experimentally and computationally investigate dynamical behaviors in coupled chemical oscillators. These networks of chemical oscillators are created using catalytic Ru(bpy)₃²⁺ loaded cation exchange beads submerged in catalyst-free Belousov-Zhabotinsky (BZ) solutions. Various network structures are created by utilizing the photosensitive nature of the Ru(bpy) ₃²⁺ catalyst. The response of the oscillators due to light stimuli can be characterized by constructing a phase response curve (PRC). The PRC quantifies the excitatory and inhibitory responses of BZ oscillators due to applied light perturbations as a function of the oscillators' phase. Different initial concentrations of reactants in the BZ reaction …

Electrochemical And Mass Spectrometry Methods For Identification Of Gunshot Residues (Gsr) In Forensic Investigations, Kourtney A. Dalzell

Graduate Theses, Dissertations, and Problem Reports (ETD)

Gun violence continues to be one of most significant challenges straining the USA society causing thousands of human lives lost every year. In 2020 alone, firearm-related incidents including homicide, accidents, and suicides, reached a staggering number of over 43,000.^1,2 With the increase in these types of incidents, several service areas in crime laboratories are heavily impacted by the number of cases run on a yearly basis. These include firearm examinations, gunshot residue (GSR) analysis, bullet hole identification, and shooting distance determination, which are crucial to support a criminal investigation and, overall, the justice system in our country. These areas …

Study Of Resonantly Stabilized Radicals In Combustion Environments, James H. Lee

Graduate Theses, Dissertations, and Problem Reports (ETD)

Resonantly stabilized radicals (RSRs) play an important role in combustion environments due to their high stability resulting from resonance. Many RSRs such as the propargyl, allyl, or benzyl radicals are precursors to the formation of polycyclic aromatic hydrocarbons (PAHs), which can aggregate to form soot. Due to their stability, these RSRs can accumulate in combustion environments in significant quantities. The primary way these radical species are consumed in flames or by reactions with other abundant radicals, by self-recombination of propargyl to form benzene, or in the form of other abundant radicals such as the hydroxyl radical. Experimentally determining the pathways …

Development Of Capillary Vibrating Sharp-Edge Spray Ionization For Improving Continuous Flow Mass Spectrometry Analysis, Chong Li

Graduate Theses, Dissertations, and Problem Reports (ETD)

Capillary Vibrating Sharp-Edge Spray Ionization (cVSSI) is new ionization technique developed in the year of 2018. This ionization technique has attractive features such as simplicity, compactness, ease of manipulation, low costs, compatible with continuous flow, etc. However, the development of high performance cVSSI for mass spectrometry analysis is a process that needs unremitting optimizations. In this dissertation, I demonstrate the development of cVSSI for improving continuous flow mass spectrometry analysis. The chapter 2 focuses on improving the ionization efficiency of cVSSI through reducing the droplet size. Three strategies were tested to reduce the droplet size of VSSI. The most effective …

Synthetic Methods For Improved Scope And Efficiency Of Copper-Catalyzed Regioselective Alkene Boracarboxylation, Steven William Knowlden

Graduate Theses, Dissertations, and Problem Reports (ETD)

The synthesis of carboxylic acids is important to the chemistry community, owing to the broad applicability of these compounds as fine chemicals and pharmaceuticals. Method development over the last decade has focused on the preparation of carboxylic acids through transition metal catalysis utilizing CO₂ as a C1 synthon. Copper-catalyzed heteroelement(bora and sila)-carboxylation protocols provide functional group rich carboxylic acid products, yet remain underdeveloped and thus underutilized. Consequently, catalytic reductive difunctionalization methodologies in which CO₂ and B(pin) (pin = pinacolate: 2,3-dimethyl-2,3-butanediolate) are installed across the double bond of a vinyl arene were recently developed. These boracarboxylation protocols provided novel, …

Advancing Compound Detection And Identification Using Vibrating Sharp-Edge Spray Ionization, Anthony Paul Debastiani

Graduate Theses, Dissertations, and Problem Reports (ETD)

Advancing Compound Detection and Identification Using Vibrating Sharp-Edge Spray Ionization

Anthony Paul DeBastiani

‘Omics consists of various areas, including genomics, proteomics, lipidomics, and metabolomics with a goal of detection and identification of biomolecules present within each of these classes within an organism. Current omic analytical methods include the use of mass spectrometry (MS) coupled with various separation techniques, including liquid chromatography (LC), with the use of heated nebulization gas assisted electrospray ionization (HESI). Although the rapid progress in LC-MS platform development has lead to significant enhancements in omic studies, significant limitations in the detection and identification of low abundant species …

Identifying And Minimizing Sources Of Variability Within Modern Spectroscopic Techniques For The Forensic Analysis Of Glass, Oriana Christy Ovide

Graduate Theses, Dissertations, and Problem Reports (ETD)

Broken glass is a trace material frequently found at crime scenes such as hit-and-runs, burglaries, assaults, and homicides. Existing research encompassing the forensic analysis of glass evidence is vast. Published studies cover the analysis and interpretation of various types of glass. However, organizations such as the National Institute of Justice (NIJ), National Institute of Standards and Technology Organization of Scientific Area Committees (NIST-OSAC), and American Society of Trace Evidence Examiners (ASTEE) continue to identify glass-specific research needs to strengthen the scientific foundations of the field. Current gaps within the forensic glass community involve understanding modern glass formulations, re-evaluating the performance …

Synthesis And Cyclotrimerization Of Sulfonyl Enynes, Alexa C. Martin

Graduate Theses, Dissertations, and Problem Reports (ETD)

The synthesis of complex, polysubstituted aromatic rings from simple, non-aromatic building blocks is a consistent challenge to the synthetic community. Neopentylene ring fusions are found in several natural products but are largely absent from synthetic compound libraries. This discrepancy reflects the limitations in modern chemical synthesis. Utilizing, in part, a thoroughly developed fragmentation/olefination methodology from the Dudley Lab, a library of novel 1-sulfonyl-1,6-enynes have been developed. In this methodology, they are prepared in three steps from dimedone (5,5-dimethyl-1,3-cyclohexanedione), an inexpensive starting material. A total of 14 novel 1-sulfonyl-1,6-enynes were synthesized. These substrates were subjected to a novel benzannulation reaction based …

Multifunctional Organoboron Compounds And Boralactonate Salts, Randika T. Abeysinghe

Graduate Theses, Dissertations, and Problem Reports (ETD)

Organoboron compounds have gathered an important significance within the chemistry community on account of their wide range of applications in synthesis, catalysis, and medicinal chemistry. Even though the uses of boron compounds in drug discovery have been overlooked until the last several decades, boronic acid containing molecules have garnered increased attention due to the unique chemical properties of the boron center. Boron-functionalized ��-aryl propionic acid non-steroidal anti-inflammatory drug derivatives (bora-NSAIDs) can be accessed via copper(I)-catalyzed alkene boracarboxylation, using CO2 and B2pin2. To explore and expand the current synthetic and future medicinal chemistry applications of these bora-NSAIDs, methods …

Heterogeneous Oxidation Of Multi-Component Aqueous Organic Aerosols: The Effect Of Transport Phenomena And Reaction Compartment On Reaction Kinetics., Tadini Wenyika Masaya

Graduate Theses, Dissertations, and Problem Reports (ETD)

The surface-bulk partitioning of small organic molecules in aqueous droplets was investigated using molecular dynamics. The air-particle interface was modeled using a 80-Å cubic water box containing series of organic molecules and surrounded by gaseous OH radicals. The properties of the organic solutes within the interface and the water-bulk were examined at a molecular-level using density profiles and radial pair distribution functions. Molecules containing only polar functional groups such as urea and glucose are found predominantly in the water bulk, forming an exclusion layer near the water surface. Substitution of a single polar group by an alkyl group in sugars …

Synthesis, Characterization, And Activation Of Pyridine Dipyrrolide Supported Vanadium-Nitrogen Multiple Bonds, Jordan Cruz Martinez

Graduate Theses, Dissertations, and Problem Reports (ETD)

The chemistry of coordination complexes of vanadium supported by pyridine di-pyrrolide pincer ligands was probed via the synthesis and investigation of a variety of compounds from the trivalent starting material, (^MesPDP^Ph)VCl(thf)₂. Under reducing conditions and subsequent addition of terpyridine, a redox transfer series (1-, 0, 1+) stemming from the neutral product (^MesPDP^Ph)V(terpy) was isolated and characterized by X-ray crystallography. The precise bond lengths, in conjunction with bulk magnetic susceptibility, allowed for a detailed study of the redox non-innocence of polypyridyl ligands in these systems.

Metathesis of the halide starting material …

2021 West Los Angeles Data Summary, Gary Bishop

Fuel Efficiency Automobile Test Publications

Simple data summary for 2021 West Los Angeles on-road emission measurements.

Development Of A New Spe Uplc–Ms/Ms Method For Extraction And Quantitation Of Toluene Diamine On Gloves Following Toluene Diisocyanate Exposure, Asma Daoud, Pierre-Luc Cloutier, Sébastien Gagné, Livain Breau, Jacques Lesage

Études primaires

Rationale

Toluene diisocyanate (TDI) is a highly reactive isocyanate commonly used as a mixture of 2,4- and 2,6- isomers in the production of flexible foams. Exposure to TDI occurs primarily through vapour inhalation in workplaces where TDI is produced or used, but dermal exposure is also possible during some tasks. To ensure workplace safety, accurate monitoring of TDI and toluene diamine (TDA) levels is required. Methods of quantifying field effectiveness of gloves in preventing dermal exposure have not been established. Therefore, there is a need to develop a new practical method for assessing glove effectiveness for TDI/TDA.

Method

A new …

On-Road Vehicle Emission Measurements And Their Use In Evaluating Emission Control Effectiveness {Presentation}, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Influence Of Dissolved Organic Matter On Phosphate Interactions With Hydrous Ferric Oxides, Alaa Hasan Alsherbi

Theses and Dissertations (Comprehensive)

Phosphorus, iron oxides, and dissolved organic matter (DOM) are components present in all aquatic systems. Excess amounts of phosphorus in aquatic systems have the potential for toxic effects, in particular, contributing to eutrophication. Most of the previous studies performed looked at the surface complexation of inorganic phosphate anions (P) to mineral surfaces such as hydrous ferric oxide (HFO). However, the role of DOM on the interactions between HFO and P is unknown. This study investigates the influence of DOM on the surface complexation of P onto HFO surfaces. Moreover, this study looks at the possibility of cation bridging formation (Ca …

The Art Of Poetry And Its Place In The History Of The Coordinating Research Councils Real World Emissions Workshop {Poster}, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

2022 Oakland Ca Data Summary, Gary Bishop

Fuel Efficiency Automobile Test Publications

Simple data summary for 2022 on-road vehicle emission measurements from Oakland CA.

Hydrophobically Modified Isosorbide Dimethacrylates As Biomaterials For Bisphenol A Free Dental Fillings, Bilal Marie

Dissertations

Amalgam and Bisphenol A glycerolate dimethacrylate (BisGMA) are the main dental filling materials in use today. Because of the negative perception of amalgam and its lower esthetic appeal, as well as the desire to replace the endocrine disruptor Bisphenol A, which is the building block of BisGMA, there has been a critical need to search for safer alternatives to these dental filling materials.

Isosorbide is a sugar-based molecule generally recognized as safe. It has been extensively studied as a replacement to the Bisphenol A core in various materials. However, isosorbide is extremely hygroscopic, and water uptake in dental fillings causes …

Fluorescence Probes For Bioimaging: Synthesis, Photophysical Properties And Applications, Mehrun Nahar Uddin

Dissertations

Fluorescent probes are a vital tool in the study of cell imaging. There are many types of fluorescent probes ranging from inorganic and organic nanoparticles to organic molecules. When used judiciously, they can help provide essential information on cellular structure and function. The introduction of two-photon microscopy has expanded the need for new probes, in particular near-infrared (NIR) absorbing and emitting fluorescent probes. The photochemical and photophysical properties of NIR probes play a crucial role in their effectiveness in cell imaging by both conventional and two-photon excitation (2PE) microscopy. In this research, the synthesis, photophysical properties, and two-photon absorption (2PA) …

Bodipy Based Photodynamic Therapy And Potassium Probes, Xiangshan Liu

Dissertations

Boron dipyrromethene (BODIPY) has become more and more popular in photophysical and biological applications. BODIPY based fluorescence compounds have numerous advantage properties including low toxicity, high absorption extinction coefficients, high fluorescence quantum yields, sharp fluorescence emissions, and resistance to photobleaching. All the good properties lead to the wide applications of BODIPY based compounds. In this research, two different kinds of BODIPY are synthesized. Firstly, BDBrC containing carbazole and BODIPY core is synthesized. Cellular uptake research shows BDBrC can target on lysosome and singlet oxygen generation research result indicates that BDBrC can be used in photodynamic therapy. BDBrC also shows pH-sensitive …

Optical And Chemical Properties Of Fragaria Ananassa And Galena: Potential Photosensitizers In A Natural Dye-Sensitized Solar Cell, Ibukun S Akinsola, Aderemi B Alabi, Coppede Nicola

Tanzania Journal of Science

Dye is one of the major components for high power conversion efficiency in a dye-sensitized solar cell. There are challenges natural dyes encounter, especially with quick degradation of the dye molecules. This work considered mineral dye in comparison with plant dye to address the challenge of degradation of natural plant dyes. The optical properties and functional groups of the two natural dyes were studied in this work. The absorption spectra, the optical band gaps and the absorption coefficients of the dyes were reported and found to be suitable for use as photosensitizers in a dye-sensitized solar cell (DSSC), as they …

Physico-Chemical Properties Of Mechanically Extracted Banana Juice At Different Ripening Stages, Mathayo G Mathias, Lilian D Kaale, Oscar Kibazohi

Tanzania Journal of Science

This paper presents the findings of a study on physico-chemical properties of low viscosity banana juice from five banana cultivars: Pisang Awak (PSA) an ABB genome, Yangambi km5 (YKM5) an AAA genome and cultivars from AAA-EA genome, namely Mbilabile, Ndeshi and Mlonga. Low viscosity banana juice was extracted using improved mechanical method at five ripening stages. The physico-chemical properties significantly varied according to cultivars and ripening stages (p < 0.05). Yields, total soluble solids (TSS), titratable acidity (TA) and pH were in the range of 19.50–74.03%, 7.33–27.64 ºBrix, 0.37–0.76% malic acid equivalent and 4.09–4.70, respectively. Yields decreased in the order of Mbilabile > Ndeshi > Mlonga > YKM5 > PSA whereas the total soluble solids increased as follows Mlonga < Mbilabile < Ndeshi < YKM5 < PSA. Furthermore, ashes and mineral contents decreased with ripening stages whereas the low viscosity banana juice was rich in potassium and magnesium. Finally, the study recommends stage 5 of the ripeness as ideal for producing low viscosity banana juice. Keywords: Mechanical extraction, Banana cultivar, Ripening stage, Tannin, Banana juice.

Effects Of Ripeness And Blending Speed On The Extraction Yield And Physical Chemical Properties Of Low Viscosity Banana Juice, Oscar Kibazohi, Victor V Matabura

Tanzania Journal of Science

Low viscosity banana juice can be extracted from banana by blending and pressing the resulted semi-solid pulp to separate the juice. This juice extraction technology is relatively new and further studies to understand key parameters for juice release is vital for scaling up production and commercialisation. This study, investigated the influence of blending speed and ripeness stage on banana juice yield using two banana cultivars; the East African highland banana (Mbile) and the exotic banana (Pisang awak). Types of sugars and organic acids in the juice were analysed using an HPLC. Changes with ripening of fruit firmness, juice pH and …

Mathematical Characterization Of Biological Control Of Cassava Pests Model, Yidiat O. Aderinto, Faith O. Ibiwoye, Michael O. Oke, Folashade M. Jimoh

Tanzania Journal of Science

Pests are major constraints to the effective growth and development of every crop through their damage, and can be controlled effectively by the use of their natural enemies which is referred to as the biological pest control. In this study, the biological control model of cassava pests through optimal control theory was presented in order to minimize the population of the pests and stabilize the natural enemies population so as not to affect the crop negatively. A mathematical model was formulated via the Lotka-Volterra model, and the model was characterized. The optimality system was established, the equilibrium point with its …

Temperature Effects On The Corrosion Inhibition Of Mild Steel In Sulfuric Acid Solution By Acacia Senegal Gum With Halide Ions, Jovine Emmanuel, Joseph Buchweishaija

Tanzania Journal of Science

The effects of temperature on the inhibitive effect of naturally occurring Acacia senegal gum exudate on the corrosion of mild steel in sulfuric acid was studied between 35 and 70 °C using electrochemical impedance spectroscopy and potentiodynamic polarization methods. Findings showed that Acacia senegal gum exudate decreases the corrosion rate of mild steel. The inhibition efficiency declined with raising temperature above 35 °C. The increase in the corrosion rate with increasing temperature was observed for both uninhibited and inhibited systems. Addition of halide ions to the Acacia senegal gum exudate solution enhanced the corrosion inhibition efficiency because of synergistic effects, …

Characterization Of The Ch Addition Product From Meta- And Ortho-Xylene + Ch Reaction And Direct Experimental Observation Of The Tetrabromine Cluster Br4 Using Synchrotron Photoionization Mass Spectrometry, Rory R. Mcclish

Master's Theses

This thesis is centered on the use of a unique gas-phase spectroscopy technique to characterize products and elucidate reaction mechanisms. Experiments were carried out at the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source located at the Lawrence Berkeley National Laboratory in Berkeley, CA. Computational work was performed on the scientific supercomputer at USF to supplement experimental findings. Chapter 1 contextualizes the work spurred in response to the deleterious interactions of anthropogenic emissions on Earth’s climate. Chapter 2 describes the theoretical manipulations foundational to the experimental design and interpretation. Chapter 3 delves into the physical details of the experimental …

The Inhibition Activity Of Tert-Butylhydroquinone Towards Corrosion Of Aluminum, Copper And Stainless Steel In Biodiesel Blend B20 Alternative Fuel, Chaza Joumaa, Ibtissam Saad, Ghassan Younes

BAU Journal - Science and Technology

Tert-butylhydroquinone (TBHQ) has been investigated as corrosion inhibitor for aluminum; copper and stainless steel in biodiesel blend B20 by using electrochemical impedance spectroscopy (EIS) method. The results showed that the inhibition efficiency increases with an increase in the concentration of TBHQ but decreases with increasing temperature from 30℃ to 60℃. A maximum inhibition efficiency of about 61.52% for aluminum was recorded for THBQ in biodiesel blend B20 at temperature 30℃ and at a concentration of 4x10^-6 M which is the lowest concentration used compared to the concentrations of TBHQ used for the other metals (copper and stainless steel). Theoretical …