Physical Chemistry Commons^™

Mechanisms Of Formation Of Novel Guanine-Guanine Cross-Links As Major End Products During One-Electron Oxidation Of Guanine Derivatives, Evan Dunn

Undergraduate Honors Theses

Guanine (G), as the most oxidizable base in DNA, is the major focus of studies of oxidation damage to DNA. The present thesis reports the first detailed characterization of G dimerization products potentially resulting from recombination of neutral G• radicals. Previous research has discovered a novel type of products of G• dimerization, D1 and D2, formed from one-electron oxidation of G derivatives. However, the mechanism of this dimerization remains elusive. While there appears to be a tautomeric equilibrium between two forms of G•, G(N₁-H)• or G(N₂-H)•, it remains unclear which intermediate participates in the formation of …

Oxidation Of Phenolic Aldehydes By Ozone And Hydroxyl Radicals At The Air-Water Interface, Md Sohel Rana, Marcelo I. Guzman

Chemistry Faculty Publications

Biomass burning releases highly reactive methoxyphenols into the atmosphere, which can undergo heterogeneous oxidation and act as precursors for secondary organic aerosol (SOA) formation. Understanding the reactivity of such methoxyphenols at the air–water interface is a matter of major atmospheric interest. Online electrospray ionization mass spectrometry (OESI-MS) is used here to study the oxidation of two methoxyphenols among three phenolic aldehydes, 4-hydroxybenzaldehyde, vanillin, and syringaldehyde, on the surface of water. The OESI-MS results together with cyclic voltammetry measurements at variable pH are integrated into a mechanism describing the heterogeneous oxidative processing of methoxyphenols by gaseous ozone (O₃) and …

The Statue Of Liberty Laboratory Activity: The Chemistry Of Copper, Jihyun Kim, Marcus D. Allen

Open Educational Resources

In this lab activity we observe chemical changes of copper in acidic conditions, salt water, and a mixture of lemon juice and vinegar and salt, and we discuss whether the Statue of Liberty would hold as much cultural icon today had the Lady Statue remain the original shiny brown color.

Carbon Oxidation At The Atomic Level: A Computational Study On Oxidative Graphene Etching And Pitting Of Graphitic Carbon Surfaces, Simon Schmitt

Theses and Dissertations--Mechanical Engineering

In order to understand the oxidation of solid carbon materials by oxygen-containing gases, carbon oxidation has to be studied on the atomic level where the surface reactions occur. Graphene and graphite are etched by oxygen to form characteristic pits that are scattered across the material surface, and pitting in turn leads to microstructural changes that determine the macroscopic oxidation behavior. While this is a well-documented phenomenon, it is heretofore poorly understood due to the notorious difficulty of experiments and a lack of comprehensive computational studies. The main objective of the present work is the development of a computational framework from …

Atom-Specific Activation In Co Oxidation, Simon Schreck, Elias Diesen, Jerry Larue, Hirohito Ogasawara, Kess Marks, Dennis Nordlund, Matthew Weston, Martin Beye, Filippo Cavalca, Fivos Perakis, Jonas Sellberg, André Eilert, Kyung Hwan Kim, Giacomo Coslovich, Ryan Coffee, Jacek Krzywinski, Alex Reid, Stefan Moeller, Alberto Lutman, Henrik Öström, Lars G. M. Pettersson, Anders Nilsson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We report on atom-specific activation of CO oxidation on Ru(0001) via resonant X-ray excitation. We show that resonant 1s core-level excitation of atomically adsorbed oxygen in the co-adsorbed phase of CO and oxygen directly drives CO oxidation. We separate this direct resonant channel from indirectly driven oxidation via X-ray induced substrate heating. Based on density functional theory calculations, we identify the valence-excited state created by the Auger decay as the driving electronic state for direct CO oxidation. We utilized the fresh-slice multi-pulse mode at the Linac Coherent Light Source that provided time-overlapped and 30 fs delayed pairs of soft …

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 …

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. …

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 …

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 Investigation Of The Low Temperature Combustion Of Mesitylene And Tert-Amyl Methyl Ether By Synchrotron Photoionization Mass Spectrometry, Martin Yu-Hin Ng

Master's Theses

This thesis describes the combustion experiments performed at the Chemical Dynamics Beamline of the Advanced Light Source (ALS) located at the Lawrence Berkeley National Laboratories (LBNL). The need for renewable fuel sources, the need for the study of their combustion in the contexts of homogenous charge combustion ignition (HCCI) engines can be found in Chapter 1. The components of the experimental set-up used throughout this thesis—time-of-flight mass spectrometer, Excimer laser, vacuum pumps and other components—and the components of ALS responsible in synchrotron radiation generation and processing—the linear accelerator, the booster ring, insertion devices, gas filters and monochromator are explained in …

Naio4 Oxidation Of Mussel Adhesive Protein Film And Its Corrosion Protection For Mg-1.0ca Alloy, Rui-Qing Hou, Ping-Li Jiang, Shi-Gang Dong, Chang-Jian Lin

Journal of Electrochemistry

The effect of oxidation of mussel adhesive protein (Mefp-1) film on the corrosive resistance for Mg-1.0Ca alloy was investigated by scanning electron microscopy (SEM), atom force microscopy (AFM), electron probe microanalysis (EPMA), Infrared reflection absorption spectroscopy (IRAS) and electrochemical methods. The results showed that the NaIO₄ induced oxidation of the pre-formed Mefp-1 film with porous morphology involved structural change of the DOPA group in the protein and resulted in a more uniform film with net-like morphology. The protein film without oxidation had an increasing resistance for the corrosion of Mg-1.0Ca alloy up to 7 days exposure. After oxidation, Epit …

Electrochemical Fabrication Of Two-Dimensional Flower-Like Pt Nanostructures For Methanol Electrocatalytic Oxidation, Xia Wang, Jun Hu, Yong-Jun Li

Journal of Electrochemistry

Two-dimensional flower-like Pt nanostructures (2D FPNs) were fabricated on glassy carbon substrates by galvanostatical electrochemical technique. The electrolyte was the HAuCl₄ + HClO₄ aqueous solution without addition of any structure-directing organic reagent, which made as-prepared Pt nanostructures cleaner, exhibiting much higher reactivity. Scanning electron microscopic images revealed that 2D FPNs were spherical Pt nano-flowers constructed by the smallest building blocks, nano-leaves. The number density of spherical Pt nano-flowers can be tuned by controlling the electrodeposition time. High resolution transmission electron microscopic images indicated that each nano-leaf was formed by growing along Pt(111) direction. Electrocatalytic activities of as-prepared 2D …

Pulse Electrodeposition Of Pd-Ni Alloy Nanoparticles For Electrocatalytic Oxidation Of Formic Acid, Fang-Zu Yang, Jun-Pei Yue, Zhong-Qun Tian, Shao-Min Zhou

Journal of Electrochemistry

The Pd-Ni alloy nanoparticles with nickel atomic contents of 12.0%, 16.4% and 22.6% were successfully electrodeposited from a Pd-Ni alloy electrolyte by square wave pulse plating. The alloy nanoparticles were in the spherical shape with a diameter of 50 ~ 80 nm. As the growth potential of the alloy was negatively shifted, the nickel content of the alloy was increased, and the size of the nanoparticles was almost the same, whereas the number, the degree of crosslinking and the real active area of the nanoparticles were increased. As the nickel content of the alloy nanoparticles increased, the peak current for …

Characteristics And Stability Of Oxide Films On Plutonium Surfaces, Harry Guillermo García Flores

Department of Chemistry: Dissertations, Theses, and Student Research

The oxidation of plutonium (Pu) metal continues to be an area of considerable activity. The reaction characteristics have significant implications for production use, storage, and disposition of this radiological material. Developing an accurate physical model of the structures, oxidation states, and oxygen concentration gradients present during oxidation are essential to understanding this process. Traditionally, the stable oxides of Pu have been thought to be plutonium sesquioxide (Pu₂O₃, O/Pu = 1.5, Pu³⁺) and plutonium dioxide (PuO₂, O/Pu = 2.0, Pu⁴⁺), existing in a layered structure on Pu metal. Many of the …

Enhanced [Ru(Bpy)_3]~(2+)-Mediated Oxidation Of Guanine Prompted By Dhp, Bao-Lian Zhang, Wei Hong, Bao-Yi Lu, Hong Li

Journal of Electrochemistry

The effects of dihexadecyl phosphate(DHP) and multi-walled carbon nanotubes(MWNTs) on the oxidation of guanine mediated by[Ru(bpy)3]2+ on the ITO electrode have been investigated by cyclic voltammetry and differential pulse voltammetry.The results showed that [Ru(bpy)3]2+ can mediate the oxidation.In the range from 0.01 to 0.15 mmol·L-1,peak currents for guanine oxidation mediated by [Ru(bpy)3]2+ increased with the rise of DHP concentrations.On the contrary,cationic surfactant HTAC has the ability to weaken the mediated oxidation of guanine.In addition,the oxidative mechanism of guanine mediated by [Ru(bpy)3]2+ with the participation of DHP is discussed.

The Mechanism Of Electrochemical Testing Method Under Synergistic Effect Of Nacl And Water Vapor At 600℃, Li Liu, Ying Li, Fu-Hui Wang

Journal of Electrochemistry

The existence of electrochemical reaction during the corrosion process of pure Fe under a deposit of solid NaCl in water vapor at above 400 ℃ had been detected by measuring the corrosion current using double-layer electrode.In EIS measurement,only one capacitive loop was obtained on the pure metals and this gave the information of oxide layer on them.The electrochemical impedance spectroscopy(EIS) and scanning-electron microscopy(SEM) results testified that there is a good relationship between the resistance of oxide layer Rox and the corresion reaction rate for pure metals with different oxidation times.The electrochemical technique is an effective method for studying corrosion performance …

A Theoretical Study Of Methanol Oxidation Mechanisms By Methanol Dehydrogenase Enzymes For Fuel Cell Applications, Nagesh B. Idupulapati

Doctoral Dissertations

Enzymes are considered for electrochemical generation of power in fuel cells. Methanol dehydrogenase (MDH) is one such enzyme, which has been used as an anodic catalyst for a methanol-fed biofuel cell producing enough power for small electronic device applications. In practice, however, there are power output limitations associated with this MDH fuel cell, which may potentially be eliminated or reduced if the reactivity of this enzyme during the oxidation of methanol at the molecular level is clearly understood.

Two mechanisms for the methanol oxidation process by MDH have been proposed in the literature, Addition-Elimination (A-E) and Hydride Transfer (H-T), but …

Study Of Corrosion Of Materials In The Sulfur-Iodine Hydrogen Production Cycle, Thao Trung Ho

UNLV Theses, Dissertations, Professional Papers, and Capstones

Hydrogen is of great interest since the availability of traditional fossil fuels is in decline. Strictly speaking, hydrogen is not a primary source of energy but is an energy carrier, since energy typically must be used from another source (electricity, natural gas, coal, etc.) to produce it. Of hydrogen production techniques, the Sulfur-Iodine thermochemical water splitting process (S-I cycle), which was proposed by General Atomics (GA), is promising with its simplicity and high efficiency. Most of the chemicals are recycled except water. However, the S-I cycle operates in a harsh, corrosive environment in the presence of a mixture of iodine …

Oxidation And Adsorption Of Deoxyribonucleic Acid At Highly Ordered Pyrolytic Graphite And Glass Carbon Electrode, Jianzhang Zhou, Lingling Wu, Jin Luo, Zhonghua Lin

Journal of Electrochemistry

It is shown that calf thymus DNA(CT DNA) can be adsorbed at highly ordered pyrolytic graphite(HOPG) electrode and detected by differential pulse voltammetry(DPV) and electrochemical atomic force microscopy(ECAFM). It is found that controlled potential pre-polarization influences largely the adsorption of dsDNA while it has little influence on ssDNA. It is demonstrated that ECAFM is useful to exploit adsorption of DNA at HOPGE. The pattern of adsorption of DNA at HOPG electrode that fits best with the experimental data is proposed. The results aslo shows that UV/Vis reflection spectroscopy, which has not been used in studying electrochemical behavior of DNA, is …

Oxidation Mechanism Of Hypophosphite, Dongbai Sun, Ying Jin, Hongying Yu, Dejun Yang

Journal of Electrochemistry

There exist two oxidation current peaks on the anodic polarization curve between -0.7 V and 0 V(SCE) in Na_hypophosphite solution. Peak Ⅰ (-0.55 V, SCE) , which represents the oxidation process from H 2PO - 2 to H 2PO - 3, has been studied previously. Peak Ⅱ, which is located at the potential about -0.4 V(SCE), is investigated emphatically in this paper. The results show that, peak Ⅰ and Ⅱ are corresponding to two successive steps in oxidation process of H 2PO - 2, i.e. peak Ⅱ corresponds to the oxidation process of adsorped (HPO 2) ads , an intermediate …

The Oxidation Of Hydrogen Absotbing Alloys And Its Inhibition, Suqin Wang, Baojia Xia, Geping Yin, Pengfei Shi

Journal of Electrochemistry

This paper introduces the method to judge:1)the possibility of oxidation of themetal hydride electrode in an anode process by cyclic voltammetric curves,2)the oxidation pattern ofmetal hydride electrode in oxygen atmosphere in various charged states,and 3)the inhibition ofoxidation of hydrogen absorbing alloys by certain surface treatment.

Mott G-Ratios In Rbx(Nh3)1-X And Oxidation State Of Rubidium Compounds From Xas, Juana Vivó Acrivos, K. Hathaway, A. Robertson, M. P. Klein, A. Thompson

Faculty Publications, Chemistry

The x-ray absorption spectra (XAS) of Rb metal, Rh,("JH,J, ,, 2H-NbSe2Rb111x and RbBr near the Rb K-edge have been used to ascertain that the oxidation state V of rubidium dissolved in ammonia and intt:rcalated in the layer compound is in the range 0 < V < I. Theobservededge shifts with temperature for semimctals are explainedin terms of the population of band states, and the ratio of the density states near the mobility edge over that calculated for a free electron model, i.e. the Mott ratio g, is ascertained using a semiempirical relation developed for the x-ray absorbance from Is levels to empty states ncar the mobility edge.

Mott G-Ratios In Rbx(Nh3)1-X And Oxidation State Of Rubidium Compounds From Xas, Juana Vivó Acrivos, K. Hathaway, A. Robertson, M. P. Klein, A. Thompson

Juana Vivó Acrivos

The x-ray absorption spectra (XAS) of Rb metal, Rh,("JH,J, ,, 2H-NbSe2Rb111x and RbBr near the Rb K-edge have been used to ascertain that the oxidation state V of rubidium dissolved in ammonia and intt:rcalated in the layer compound is in the range 0 < V < I. Theobservededge shifts with temperature for semimctals are explainedin terms of the population of band states, and the ratio of the density states near the mobility edge over that calculated for a free electron model, i.e. the Mott ratio g, is ascertained using a semiempirical relation developed for the x-ray absorbance from Is levels to empty states ncar the mobility edge.