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 …

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 …

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 …

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 …

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 …

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 …