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- Genre: Academic theses
Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
Description
Four Souvenirs for Violin and Piano was composed by Paul Schoenfeld (b.1947) in 1990 as a showpiece, spotlighting the virtuosity of both the violin and piano in equal measure. Each movement is a modern interpretation of a folk or popular genre, re- envisioned over intricate jazz harmonies and rhythms. The work was commissioned by violinist Lev Polyakin, who specifically requested some short pieces that could be performed in a local jazz establishment named Night Town in Cleveland, Ohio. The result is a work that is approximately fifteen minutes in length. Schoenfeld is a respected composer in the contemporary classical music community, whose Café Music (1986) for piano trio has recently become a staple of the standard chamber music repertoire. Many of his other works, however, remain in relative obscurity. It is the focus of this document to shed light on at least one other notable composition; Four Souvenirs for Violin and Piano. Among the topics to be discussed regarding this piece are a brief history behind the genesis of this composition, a structural summary of the entire work and each of its movements, and an appended practice guide based on interview and coaching sessions with the composer himself. With this project, I hope to provide a better understanding and appreciation of this work.
ContributorsJanczyk, Kristie Annette (Author) / Ryan, Russell (Thesis advisor) / Campbell, Andrew (Committee member) / Norton, Kay (Committee member) / Arizona State University (Publisher)
Created2015
Description
Samuel Máynez Prince (1886-1966), was a prolific and important Mexican musician. Prince’s musical style followed the trends of the nineteenth-century salon music genre. His compositions include lullabies, songs, dances, marches, mazurkas, waltzes, and revolutionary anthems. Prince’s social status and performances in the famed Café Colón in Mexico City increased his popularity among high-ranking political figures during the time of the Mexican Revolution as well as his status in the Mexican music scene.
Unfortunately there is virtually no existing scholarship on Prince and even basic information regarding his life and works is not readily available. The lack of organization of the manuscript scores and the absence of dates of his works has further pushed the composer into obscurity. An investigation therefore was necessary in order to explore the neglected aspects of the life and works of Prince as a violinist and composer. This document is the result of such an investigation by including extensive new biographical information, as well as the first musical analysis and edition of the complete recovered works for violin and piano.
In order to fill the gaps present in the limited biographical information regarding Prince’s life, investigative research was conducted in Mexico City. Information was drawn from archives of the composer’s grandchildren, the Palacio de Bellas Artes, the Conservatorio Nacional de Música de México, and the Orquesta Sinfónica Nacional. The surviving relatives provided first-hand details on events in the composer’s life; one also offered the researcher access to their personal archive including, important life documents, photographs, programs from concert performances, and manuscript scores of the compositions. Establishing connections with the relatives also led the researcher to examining the violins owned and used by the late violinist/composer.
This oral history approach led to new and updated information, including the revival of previously unpublished music for violin and piano. These works are here compiled in an edition that will give students, teachers, and music-lovers access to this unknown repertoire. Finally, this research seeks to promote the beauty and nuances of Mexican salon music, and the complete works for violin and piano of Samuel Máynez Prince in particular.
Unfortunately there is virtually no existing scholarship on Prince and even basic information regarding his life and works is not readily available. The lack of organization of the manuscript scores and the absence of dates of his works has further pushed the composer into obscurity. An investigation therefore was necessary in order to explore the neglected aspects of the life and works of Prince as a violinist and composer. This document is the result of such an investigation by including extensive new biographical information, as well as the first musical analysis and edition of the complete recovered works for violin and piano.
In order to fill the gaps present in the limited biographical information regarding Prince’s life, investigative research was conducted in Mexico City. Information was drawn from archives of the composer’s grandchildren, the Palacio de Bellas Artes, the Conservatorio Nacional de Música de México, and the Orquesta Sinfónica Nacional. The surviving relatives provided first-hand details on events in the composer’s life; one also offered the researcher access to their personal archive including, important life documents, photographs, programs from concert performances, and manuscript scores of the compositions. Establishing connections with the relatives also led the researcher to examining the violins owned and used by the late violinist/composer.
This oral history approach led to new and updated information, including the revival of previously unpublished music for violin and piano. These works are here compiled in an edition that will give students, teachers, and music-lovers access to this unknown repertoire. Finally, this research seeks to promote the beauty and nuances of Mexican salon music, and the complete works for violin and piano of Samuel Máynez Prince in particular.
ContributorsEkenes, Spencer Arvin (Author) / McLin, Katherine (Thesis advisor) / Feisst, Sabine (Committee member) / Jiang, Danwen (Committee member) / Arizona State University (Publisher)
Created2016