Physical Sciences and Mathematics Commons^™

The Investigation Of The Chlorine Initiated Oxidation Of 2-Phenylethanol And Stability Of Superalkali Lithium Substituted Silyls., Adam Otten

Master's Theses

This thesis investigates the combustion potential of 2-phenylethanol and the superalkali properties of small lithium substituted silicon compounds. All combustion experiments were performed at the Advanced Light Source of Lawrence Berkeley National Laboratory at the Chemical Dynamics Beamline 9.0.2. The chlorine initiated oxidation of 2PE was investigated at 298 and 550 K using a multiplex photoionization mass spectrometer, coupled with the tunable vacuum ultraviolet radiation. Reaction products were identified using kinetic time traces and photoionization spectra.

Additionally, the stability of small superalkali silicon-lithium compounds has also been investigated. All structures and energetics were calculated using the CBS-QB3 composite method.

The …

H2 Oxidation Over Supported Au Nanoparticle Catalysts: Evidence For Heterolytic H2 Activation At The Metal-Support Interface, Todd N. Whittaker, K. B. Sravan Kumar, Christine Peterson, Meagan N. Pollock, L. C. Grabow, Bert D. Chandler

Chemistry Faculty Research

Water adsorbed at the metal-support interface (MSI) plays an important role in multiple reactions. Due to its importance in CO preferential oxidation (PrOx), we examined H₂ oxidation kinetics in the presence of water over Au/TiO₂ and Au/Al₂O₃ catalysts, reaching the following mechanistic conclusions: (i) O₂ activation follows a similar mechanism to that proposed in CO oxidation catalysis; (ii) weakly adsorbed H₂O is a strong reaction inhibitor; (iii) fast H₂ activation occurs at the MSI, and (iv) H₂ activation kinetics are inconsistent with traditional dissociative H₂ chemisorption on metals. Density …

No2- And No3- Enhance Cold Atmospheric Plasma Induced Cancer Cell Death By Generation Of Onoo-, Dehui Xu, Qingjie Cui, Yujing Xu, Zhijie Liu, Zeyu Chen, Wenjie Xia, Hao Zhang, Dingxin Liu, Hailan Chen, Michael G. Kong

Bioelectrics Publications

Cold atmospheric plasma (CAP) is a rapidly developed technology that has been widely applied in biomedicine especially in cancer treatment. Due to the generation of various active species in plasma, CAP could induce various tumor cells death and showed a promising potential in cancer therapy. To enhance the biological effects of gas plasma, changing the discharging parameters is the most commonly used method, yet increasing discharging power will lead to a higher possibility of simultaneously damage surrounding tissues. In this study, by adding nontoxic concentration of additional nitrite and nitrate in the medium, we found that anti-tumor effect of CAP …

An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman

Chemistry Faculty Publications

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric transport. …

Synthesis, Characterization, And Crystal Structure Of The (Η5-C5ph5)Cr(Co)3 Radical, Ray J. Hoobler, Marc A. Hutton, Mills M. Dillard, Michael Castellani, Arnold L. Rheingold, Anne L. Rieger, Philip H. Rieger, Thomas C. Richards, William E. Geiger

Michael P. Castellani

The reaction between Cr(CO)₆ and Na(C₅Ph₅ ) in refluxing diglyme yields [Na(diglyme)_3/2][(C₅Ph₅)Cr(CO)₃], 1. Metathesis of 1 with [Ph₃P=N=PPh₃ ]Cl in CH₂Cl₂ yields [Ph₃P=N=PPh₃][(C₅Ph₅)Cr(CO)₃], 2. Oxidation of 1 by AgBF4 in cold THF under an argon atmosphere produces (C₅Ph₅)Cr(CO)₃, 3. Complexes 2 and 3 form a redox pair connected by a quasireversible one-electron process, E⁰ = -0.69 V vs ferrocene in CH₂Cl₂, …

Synthesis, Characterization, And Molecular Structure Of Bis(Tetraphenylcyclopentdienyl)Rhodium(Ii)⊗, James E. Collins, Michael Castellani, Arnold L. Rheingold, Edward J. Miller, William E. Geiger, Anne L. Rieger, Philip H. Rieger

Michael P. Castellani

A 5 day diglyme reflux of Rh(acac)3 and K(C5HPh4), followed by treatment with aqueous HPF6, produces orange-yellow [(C5HPh4)2Rh]PF66 in 40 - 50% yield. Reduction of [(C5HPh4)2Rh]PF6 with sodium amalgam in THF yields olive green (C5HPh4)2Rh in 70% yield. (C5HPh4)2Rh crystallizes in the triclinic [Error : unloaded OLE object or mail attachment]space group with unit-cell parameters of a = 8.622 (3) Å, b = 10.778 (4) Å, c = 12.894 (5) Å, a = 65.58 (3)°, b = 72.66 (3)°, g = 83.52 (3)°, and Z = 1. The least squares data refined to RF = 7.63% and …

Oxidation Of Benzylic Alcohols And Lignin Model Compounds With Layered Double Hydroxide Catalysts, Justin K. Mobley, John A. Jennings, Tonya Morgan, Axel Kiefer, Mark Crocker

Chemistry Faculty Publications

Alcohol oxidation to carbonyl compounds is one of the most commonly used reactions in synthetic chemistry. Herein, we report the use of base metal layered double hydroxide (LDH) catalysts for the oxidation of benzylic alcohols in polar solvents. These catalysts are ideal reagents for alcohol oxidations due to their ease of synthesis, tunability, and ease of separation from the reaction medium. LDHs synthesized in this study were fully characterized by means of X-ray diffraction, NH₃-temperature programmed desorption (TPD), pulsed CO₂ chemisorption, N₂ physisorption, electron microscopy, and elemental analysis. LDHs were found to effectively oxidize benzylic alcohols …

Photochemical Investigation Of High-Valent Metal-Oxo Intermediates Containing Corrole And Light-Harvesting Porphyrin Ligands, Jonathan Malone

Masters Theses & Specialist Projects

In enzymatic and synthetic catalytic oxidations, high-valent iron-oxo intermediates play a vital role as the active oxidant. In this regard, many synthetic metal catalysts are designed as biomimetic models to resemble the active site of Cytochrome P450 enzymes (P450) which are the predominant oxidation catalysts in nature. Vitamin B12 cofactors, with a corrole-like structure corrin, are also utilized in some of the more difficult reactions in nature such as rearrangement and reductase reactions.

In this work, application of the promising photochemical method to corrolecontaining ligands systems showed much success in the generation of manganese(V)-oxo corrole intermediates using two electron-deficient corrole …

A Multi-Size Study Of Gold Nanoparticle Degradation And Reformation In Ceramic Glazes, Nathan Nl. Dinh, Luke T. Dipasquale, Michael C. Leopold, Ryan H. Coppage

Chemistry Faculty Publications

Most traditional ceramic glazes employ high amounts of transition metal colorants that are toxic to the environment and can cause health issues in humans through surface leaching. Gold nanoparticles (Au-NPs) have been found to be environmentally friendly and non-toxic alternative metal colorant in ceramic glazes. The plasmon band observed with Au-NPs can result in vibrant solutions by manipulating NP size, shape, and concentration; however, the effects of traditional firing in both reductive and oxidative kilns on Au-NPs are poorly understood. Aside from ancient art processes whose mechanisms have not been fully explored, the use of Au-NPs as suspended ceramic glaze …

Pyrolysis Of Jet Propellants And Oxidation Of Polycyclic Aromatic Radicals With Molecular Oxygen: Theoretical Study Of Potential Energy Surfaces, Mechanisms, And Kinetics, Daniel E. Belisario-Lara

FIU Electronic Theses and Dissertations

Two reaction classes have been studied computationally including the pyrolysis of various components of airplane fuels, such as decane, dodecane, butylbenzene isomers, and JP-10 (exo-tetrahydrodicyclopentadiene), and oxidation of a group of molecules belonging to the class of Polycyclic Aromatic Hydrocarbons (PAHs). Investigation of both reaction classes have been performed using ab initio quantum chemistry methods with the Gaussian 09 and MOLPRO programs at various levels of theory. Initially, Potential Energy Surfaces (PES) were generated at the G3(MP2,CC)/B3LYP/6-311G** level of theory for various radicals involved in the reactions as reactants, intermediates, transition states, and products. The next step was …

Determination Of The Oxidative Capacity Of Soot Toward Gsh And Characterization Of Soot Physicochemical Properties, Kaylee Troth

All Master's Theses

Fine atmospheric particulate matter (PM_2.5) emitted during the combustion of fossil and biomass fuels is known to adversely affect human health. While the underlying mechanisms are thought to be driven by the generation of reactive oxygen species (ROS), specific particle characteristics responsible for this detrimental effect are not well understood. In this research, the quantitative determination of the biologically relevant antioxidant, glutathione (GSH), was optimized for use as an indicator of oxidative stress to shed light on relevant particle characteristics. This was accomplished via fluorescent spectroscopy for GSH determination by way of reaction with o-phthalaldehyde (OPA), a …

Kinetics Of Silver(I)-Catalyzed Oxidation Of Allyl Alcohol By Peroxodiphosphate Inacetate Buffers, Priyamvada Sharma, Riya Sailani, Deepmala Pareek, Chandra Lata Khandelwal

Turkish Journal of Chemistry

The kinetics and mechanism of silver(I)-catalyzed oxidation of allyl alcohol with peroxodiphosphate in acetate buffers have been studied. The rate is independent of allyl alcohol concentration. The effect of other reaction parameters such as hydrogen and acetate ions has also been studied. The rate law accounting for all experimental observations corresponds to the proposed mechanism. The energy and entropy of activation have also been evaluated by employing Eyring plots.

Analysis Of Oxidation Of Carbon Monoxide On Rh (110), Razan Tanbour

Senior Honors Theses and Projects

81% of all rhodium (Rh) is used in automobile catalytic converters. Consequently, researchers have dedicated a lot of effort into understanding the behavior of nonmetal oxides on a Rh surface. Using a computer simulation program, we have studied the absorption and oxidation of carbon monoxide (CO) on a terraced Rh surface (lattice) with a width of three and a height of 10000 using a mechanism that describes the behavior at low temperatures. Varying the reaction activation energies (rate constants), and the mobility of the CO, led to changes in the surface coverages of oxygen and CO. Specifically, increasing the activation …

Oxidation Of Dibenzothiophene To Dibenzothiophene-Sufone Using A Molybdenum (Vi) Oxide Catalyst: A Kinetic Study Testing Solvent Dependency And Mole Ratio Efficiency, Tomas Trevino Jr.

Theses and Dissertations

Oxidative desulfurization (ODS) is currently a solution to hydrodesulphurization. Currently, industrial usage of hydrodesulphurization (HDS) is the common source for petroleum purification. Unfortunately, HDS comes with environmental and economical ramifications. Due to the problems and potential hazards being presented with HDS, ODS has become a topic of interest in research development. A kinetic study using molybdenum (VI) oxide as a catalyst was used in oxidative desulfurization. Factors such as mole ratio and solvent dependency were tested for efficiency. As activation energy was calculated to show maximum efficiency with respect to temperature and concentration. Gas Chromatography, FT-IR, and Mass Spectroscopy were …

Air-Oxidation Of Phenolic Resin Aerogels: Backbone Reorganization, Formation Of Ring-Fused Pyrylium Cations, And The Effect On Microporous Carbons With Enhanced Surface Areas, Hojat Majedi Far, Suraj Donthula, Tahereh Taghvaee, Adnan Malik Saeed, Zachary Garr, Chariklia Sotiriou-Leventis, Nicholas Leventis

Chemistry Faculty Research & Creative Works

This paper is a thorough investigation of the chemical transformations during pyrolytic conversion of phenolic resins to carbons, and reports that all carbons obtained from main-stream phenolic resins including phloroglucinol-formaldehyde (FPOL), phloroglucinol-terephthalaldehyde (TPOL), resorcinol-formaldehyde (RF), and phenol-formaldehyde (PF) contain fused pyrylium rings and charge-compensating phenoxides. Those four phenolic resins were prepared via a fast HCl-catalyzed process as low-density nanostructured solids classified as aerogels, which, owing to their open porosity, allowed air circulation through their bulk. In that regard, the first step of this study was the air-oxidation of those phenolic resin aerogels at 240 °C. In FPOL and TPOL aerogels, …

The Oxidation State Of Hawaiian Magmas, Michael Vollinger

Masters Theses

In order to estimate the oxygen fugacity of Hawaiian lavas I have measured the ferric/ferrous ratios of samples from the 1984 eruption of Mauna Loa volcano and from the ongoing (1983-2017) Puu Oo eruption of Kilauea volcano. Fifteen samples were studied from the 21 day Mauna Loa eruption and 86 samples, erupted between 1983 and 2004, of the 34 year long Kilauea eruption. Both studies show that, in order to obtain reliable estimates of oxygen fugacity when, where, and how basaltic lava is sampled is of critical importance. Water-quenched lavas and spatter sampled at, or near vents, are less oxidized …

Interaction Between Air Plasma-Produced Aqueous 1o2 And The Spin Trap Dmpo In Electron Spin Resonance, Chen Chen, Fanying Li, Hai-Lan Chen, Michael G. Kong

Bioelectrics Publications

A series of electron spin resonance (ESR) experiments is done to quantitatively measure the concentrations of aqueous ¹O₂ and OH produced by a surface micro-discharge air plasma device. ¹O₂ is tested to be existed in the plasma treated solution by using the spin trap of TEMP. However, the unexpected DMPOX spectrum is observed in measuringOH by the spin trap of 5,5-Dimethyl-1-Pyrroline-N-Oxide (DMPO). With more chemical scavenger experiments, it is found that removal of aqueous ¹O₂ leads to the disappearance of DMPOX in ESR. Therefore, the generation of DMPOX is directly related to the oxidation …

Catalytic Oxidation And Depolymerization Of Lignin In Aqueous Ionic Liquid, Lalitendu Das, Siquan Xu, Jian Shi

Biosystems and Agricultural Engineering Faculty Publications

Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C₂C₁Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H₂O₂ as oxidizing agent in a batch reactor. CoCl₂ and …

A Chlorine-Free Protocol For Processing Silicon, Germanium, And Tin, Michael J. Krause

Electronic Thesis and Dissertation Repository

Replacing molecular chlorine and hydrochloric acid with less energy- and risk-intensive reagents would dramatically improve the environmental impact of metal manufacturing at a time when demand for metals is rapidly increasing. Germanium and tin are classified as “critical” elements based on growing demand for these elements in technological applications, lack of suitable substitutes, and, for germanium, high dispersion in the environment making extraction of the element process-intensive. This thesis describes a recyclable quinone / catechol redox platform that provides an innovative replacement for elemental chlorine and hydrochloric acid in the conversion of germanium metal or tin metal to element tetrachloride …

The Investigation And Characterization Of The Reaction Of 2-Methylfuran And 2-Methyl-3-Buten-2-Ol With O(3p) And The Photodissociation Of Xylyl Bromide Isomers, Yasmin Fathi

Master's Theses

This thesis has studied the oxidation behavior of different biofuels or additives, 2-methyl-3-buten-2-ol and 2-methylfuran, in combustion experiments at the Chemical Dynamics Beamline held at the Advanced Light Source of the Lawrence Berkley National Laboratory. The oxidation of these fuels were initiated through O(³P) and the combustion experiments were analyzed using a multiplexed chemical kinetics photoionization mass spectrometer with tunable synchrotron radiation. Products of the different reactions were identified using kinetic profiles and further characterized using the photoionization spectra. The amount of each species was calculated using branching fractions.

Additionally, the unimolecular dissociation of the xylyl bromide isomers …

Homogeneous Ligand-Centered Hydrogen Evolution And Hydrogen Oxidation : Exploiting Redox Non-Innocence To Drive Catalysis., Andrew Z. Haddad

Electronic Theses and Dissertations

Hydrogen is a promising carbon-free fuel / energy carrier and is an essential building block for many industrial and agricultural processes. Rising energy demands have ignited interest in the development of carbon-free and carbon neutral energy sources. In this context, hydrogen is an attractive candidate—being energy-dense, carbon-free—and easily accessible through a two-electron reduction of water. Accordingly, many electrochemical homogeneous catalyst systems have been studied, with a focus on understanding the mechanism of hydrogen evolution proceeding through metal-hydride intermediates. However, there has been a renaissance in hydrogen evolution reaction (HER) catalyst design, with many groups implicating ligand redox non-innocence as a …

Nitrate Radicals And Biogenic Volatile Organic Compounds: Oxidation, Mechanisms And Organic Aerosol, Nga Lee Ng, Steven S. Brown, Alexander T. Archibald, Elliot Atlas, Ronald C. Cohen, John N. Crowley, Douglas A. Day, Neil M. Donahue, Juliane L. Fry, Hendrik Fuchs, Robert J. Griffin, Marcelo I. Guzman, Hartmut Hermann, Alma Hodzic, Yoshiteru Iinuma, José L. Jimenez, Astrid Kiendler-Scharr, Ben H. Lee, Deborah J. Luecken, Jingqiu Mao, Robert Mclaren, Anke Mutzel, Hans D. Osthoff, Bin Ouyang, Benedicte Picquet-Varrault, Ulrich Platt, Havala O. T. Pye, Yinon Rudich, Rebecca H. Schwantes, Manabu Shiraiwa, Jochen Stutz, Joel A. Thornton, Andreas Tilgner, Brent J. Williams, Rahul A. Zaveri

Chemistry Faculty Publications

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO₃) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO₃-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number …

The Decline And Recovery Of Thermal Oxidative Stability Of Ultra-Low Sulfur Diesel Blends, Abigail Schoor Cohen

Electronic Theses and Dissertations

Dissertation supervised by Professor Bruce D. Beaver

The oxidative stability of ultra-low sulfur diesel (ULSD) has generally been expected to continuously decline over time. However, recent studies have suggested that it may fluctuate.^1-2 In this study, the oxidative stability of stored commercially purchased ULSD was monitored with a methanol extraction method.³ In this methodology, proposed by Hardy and Wechter, fuel blends are extracted with methanol before and after thermal stressing.⁴ The methanol-soluble layer contains the oxygenated and oxidizable components of the fuel (SMORS) and the change in this mass upon stressing thus represents the oxidative stability of …

Singlet Oxygen Generation From Poly[4-Diacetoxyiodo]Styrene And Hydrogen Peroxide, Mustafa Çatir

Turkish Journal of Chemistry

Treatment of hydrogen peroxide with a polymer-supported hypervalent iodine compound, poly[4-diacetoxyiodo] styrene (PDAIS), generates singlet molecular oxygen ($^{1}$O$_{2})$. Singlet oxygen generation was proved by trapping with typical organic compounds such as conjugated dienes, aromatic dienes, and electron-rich alkene. When compared to monomer analogue, the use of PDAIS in peroxidation of substrates gave slightly better yields (45%-96%). Regeneration and reuse of PDAIS showed similar activity. The mechanism underlying generation of singlet oxygen and reaction scope was examined.

Preventing Oxidation Of Aluminum Films With Cadmium Of Zinc Barriers, Spencer B. Perry

Student Works

The planned Large UV/Optical/Near-infrared Telescope (LUVOIR) is expected to launch sometime in the 2030s if NASA surveys recommend LUVOIR over several other projects in early developmental stages [1]. As the project title suggests, the proposed telescope would include large mirrors (between 8 and 16 meters) as part of the orbiting reflector telescope. My research focused on the preparation of aluminum mirrors with zinc or cadmium barrier layers that were designed to prevent oxidation of the aluminum.

The Use Of Sodium Persulfate In Hydraulic Fracturing Fluids: A Degradation Study Based On Furfural, Katherine Elizabeth Manz

Masters Theses

Hydraulic fracturing has allowed natural gas to become a viable energy source via extraction of unconventional shale reserves, but this process requires an enormous amount of water. To ensure a productive fracture, a proprietary blend of chemical additives is added to the water. In this research, a hydraulic fracturing chemical additive – an enzyme breaking agent – is analyzed for organic components using gas chromatography mass spectrometry. The chemical changes that occur over the course of a fracture are also investigated using one model chemical found in the additive, furfural, in order to help assess the environmental risk that hydraulic …

Biomimetic Tools In Oxidative Metabolism: Characterization Of Reactive Metabolites From Antithyroid Drugs, Kudzanai Chipiso

Dissertations and Theses

Toxicities of sulfur-based drugs have been attributed to formation of highly reactive sulfur oxo-acids and depletion of glutathione by the formation of reactive metabolites. Metabolic activation of these sulfur centers to conceivably toxic reactive metabolites (RMs) that can covalently modify proteins is considered the initial step in drug-induced toxicity. Despite considerable effort and research, detection and characterization of these RMs during drug development and therapy remains a challenge. Methimazole (MMI) and 6-propyl-2-thiouracil (PTU) are two commonly used antithyroid, sulfur-based drugs. Though effective, these drugs are associated with idiosyncratic toxicity. PTU has acquired a black box warning and physicians are calling …

Asymmetric Α-Hydroxy Ketone Synthesis By Direct Ketone Oxidation Using A Bimetallic Palladium(Ii) Complex, Othman A. Hamed, Arab El-Qisairi, Hanan Qaseer, Emad M. Hamed, Patrick M. Henry, Daniel Becker

Daniel P. Becker

No abstract provided.

Development Of Palladium Catalyzed Alkene Difunctionalization On Vinyl-Quinoline Type Substrate And Isolation Of Pd-Alkyl Intermediate, Lusha Xu

Electronic Theses and Dissertations

The synthesis of quinoline derivatives is a continuing issue facing organic chemists in both academia and industry. To address this problem, palladium-catalyzed alkene difunctionalization was developed to be a powerful and straightforward strategy of synthetic transformations for adding diversity to organic molecules. In this thesis, Pd-catalyzed olefin difunctionalization reactions of vinyl-quinoline type substrate via generating Pd-alkyl intermediates were mainly described. The reactions described herein are pursuing three significant goals: 1) to isolate and recrystallize Pd-alkyl complexes; 2) to achieve oxidation reactions on Pd-alkyl intermediate; and 3) to investigate stereochemistry of nucleopalladation step on vinyl-quinoline starting materials.

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …