Preparative mass spectrometry is a gas-phase ion deposition technique aimed at deposition of monodisperse ion beams on a surface. This is accomplished through the implementation of a soft-landing ion mobility system which allows for high ion flux of conformationally selected ion packets. The soft-landing ion mobility system has been applied to a number of unique chemical problems including the deposition of insulators on graphene, the preparation of reusable surface enhanced Raman spectroscopic substrates, and the deposition of uranium nanoparticles. Soft-landing ion mobility provided a platform for the quick deposition of usable amounts of materials, which is the major objective of preparative mass spectrometry. Soft-landing ion mobility is unique when compared to other preparative mass spectrometric techniques in that the ion packets are conformationally separated, not separated on mass to charge ratio. This provides orthogonal complementary data to traditional mass spectrometric techniques and allows for the study of conformationally monodisperse surfaces. The diversity of problems that have been and continued to be explored with soft-landing ion mobility highlight the utility of the technique as a novel tool for the study of multiple ion/surface interactions.

The problem of this study was the comparison of the effectiveness of four selected programs of physical education in the development of physical fitness and general motor ability.

Recital presented at the UNT College of Music Recital Hall in partial fulfillment of the Doctor of Musical Arts (DMA) degree.

Recital presented at the UNT College of Music Voertman Hall in partial fulfillment of the Doctor of Musical Arts (DMA) degree.

Recital presented in Shenzhen, China in partial fulfillment of the Doctor of Musical Arts (DMA) degree.

Recital presented at the UNT College of Music Recital Hall in partial fulfillment of the Doctor of Musical Arts (DMA) degree.

This dissertation is a study involving the synthesis and chemistry of arylhaloketenes and cyclopentadiene cycloadducts, and a study of the cycloadduct isomer distribution was begun.

Sixteenth century commedia dell’arte actors relied on gaudy costumes, physical humor and improvisation to entertain audiences. the Spieltenor in the modern operatic repertoire has a similar comedic role. Would today’s Spieltenor benefit from consulting the commedia dell’arte’s traditions? to answer this question, I examine the commedia dell’arte’s history, stock characters and performance traditions of early troupes. the Spieltenor is discussed in terms of vocal pedagogy and the fach system. I reference critical studies of the commedia dell’arte, sources on improvisatory acting, articles on theatrical masks and costuming, the commedia dell’arte as depicted by visual artists, commedia dell’arte techniques of movement, stances and postures. in addition, I cite vocal pedagogy articles, operatic repertoire and sources on the fach system. My findings suggest that a valid relationship exists between the commedia dell’arte stock characters and the Spieltenor roles in the operatic repertoire. I present five case studies, pairing five stock characters with five Spieltenor roles. Suggestions are provided to enhance the visual, physical and dramatic elements of each role’s performance. I conclude that linking a commedia dell’arte stock character to any Spieltenor role on the basis of shared traits offers an untapped resource to create distinctive characterizations based on theatrical traditions.

Although the current, exhaustive studies of Brahms' works have covered many aspects of the composer's art, it is still surprising that his large-scale, five-movement Piano Sonata No.3 has in many ways been insufficiently studied by scholars who have emphasized the genre of the piano sonata and the aspect of performance practice over the work's more diverse features. Another reason that this early work has been understudied could in fact be that his later compositions in other genres, such as his symphonies, chamber music or choral music, have been perceived by scholars to represent best his most mature, comprehensive style. This dissertation will therefore examine the orchestral underpinnings of this monumental work which owes most often its already mature artistic essence to Brahms' multi-instrumental approach.

The objective of this research problem was to synthesize aldohaloketenes and investigate the chemistry of this new class of ketenes.

Duet literature remains largely untapped as a pedagogical tool in the undergraduate voice studio. This dissertation examines the ways in which eight duets for female voices, although not written primarily for pedagogical use, may be used to teach four main areas of voice technique: intonation, vocal agility, legato singing, and dramatic skills. Duets are chosen primarily from the standard repertoire and are in English, German, French, Italian and Latin. The compositional styles range from the Baroque period through the 20th century. Genres include art song, oratorio, and opera. Each chapter focuses on one of the four vocal skills listed above, and includes examinations of two duets whose vocal writing (rhythm, tessitura, intervals, tempi, and text) make them appropriate candidates for pedagogical use in the improvement of that specific skill. Both male and female teachers of singing may utilize this project as a practical resource and model in how to use other duets, including those for other voice types, for similar purposes in their teaching studio. This project also demonstrates how the experience of singing duets helps students develop ensemble singing as they listen and respond to each other. Finally, this project offers voice teachers an additional pedagogical tool to help …

The objectives of this research problem was to employ alkylhaloketene-olefin isomer distributions to aid in understanding the stereochemistry and mechanism of alkylhaloketene-olefin cycloadditions.

The kinetics of ligand substitution for CO in Co4(CO)10(mu4-PPh2) , 1, have been investigated for the ligands P(OMe)3, P(OEt)3, PPh2H, P(0-i-Pr)3, P(n-Bu)3, PPh3, P(i-Pr)3, and PCy3 over a wide temperature range.

In the early 1920s the Weimar Republic commissioned a series of new light cruisers of the Königsberg class and in July 1926, the keel of the later christened Karlsruhe was laid down. The 570 feet long and almost 50 feet wide ship was used as a training cruiser for future German naval officers. Between 1930 and 1936 the ship conducted in all five good-will tours around the world, two under the Weimar Republic and three under the Third Reich. These good-will tours or gute Willen Fahrten were an important first step in reconciling Germany to the rest of the world and were meant to improve international relations. The Foreign Office and the Ministry of Defense carefully orchestrated all stops of the vessels in conjunction with the respective embassies abroad. Final arrangements were made at least six-nine months before the scheduled visits and even small adjustments to the itinerary proved troublesome. Further, all visits were treated as “unofficial presentations.” The mission of the Karlsruhe was twofold: first to extend or renew relations with other nations, and second to foster notions of Heimat and the Germandom (Deutschtum) abroad. The dissertation is divided in two large parts; the individual training cruises with all …

This study deals with the (4+2)-cycloaddition reactions of 4-π electron compounds with ketenes. Chloroketenes were generated in situ from the corresponding chlorinated acid chlorides in the presence of the ketenophiles. Chloro-, dichloro- and diphenylketenes reacted with 1-methoxy-3-trimethylsiloxy-l,3-butadiene, and 2,4-bis(trimethylsiloxy)-1,3-pentadiene to yield the corresponding dihydropyrans. The dihydropyrans yielded substituted 4-pyranones on hydrolysis.

The tricobalt cluster PhCCo3(CO)9 (1) reacts with the bidentate phosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) in the presence of added Me3NO to give the diphosphine-substituted cluster PhCCo3(CO)7(bma) (2). Cluster 2 is unstable in solution, readily losing CO to afford Co3(CO)6[(μ2-η2/η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ2-PPh2) (3) as the sole observed product. VT-31P NMR measurements on cluster 2 indicate that the bma ligand functions as both a chelating and a bridging ligand. At -97 °C, 31P NMR analysis of 2 reveals a Keq of 5.7 in favor of the bridging isomer. The bridged bma cluster 2 is the only observed species above -50°C. The solid-state structure of 2 does not correspond to the major bridging isomer observed in solution but rather the minor chelating isomer. The conversion of 2 to 3 followed first-order kinetics, with the reaction rates being independent of the nature of the reaction solvent and strongly suppressed by added CO, supporting a dissociative loss of CO as the rate-determining step. The activation parameters for CO loss were determined to be ΔH≠ = 29.9 ± 2.2 kcal/mol and ΔS≠ = 21.6 ± 6 eu.

The capability to characterize disease states by way of determining novel biomarkers has led to a high demand of single cell and organelle analytical methodologies due to the unexpected heterogeneity present in cells of the same type. Lipids are of particular interest in the search for biomarkers due to their active roles in cellular metabolism and energy storage. Analyzing localized lipid chemistry from individual cells and organelles is challenging however, due to low analyte volume, limited discriminate instrumentation, and common requirements of separation procedures and expenditure of cell sample. Using nanomanipulation in combination with mass spectrometry, individual cells and organelles can be extracted from tissues and cultures in vitro to determine if heterogeneity at the cellular level is present. The discriminate extraction of a single cell or organelle allows the remainder of cell culture or tissue to remain intact, while the high sensitivity and chemical specificity of mass spectrometry provides structural information for limited volumes without the need for chromatographic separation. Mass analysis of lipids extracted from individual cells can be carried out in multiple mass spectrometry platforms through direct-inject mass spectrometry using nanoelectrospray-ionization and through matrix-assisted laser/desorption ionization.

Applications of computational quantum chemistry are presented, including an analysis of the photophysics of cyclic trinuclear coinage metal pyrazolates, an investigation into a potential catalytic cycle utilizing transition metal scorpionates to activate arene C-H bonds, and a presentation of the benchmarking of a new composite model chemistry (the correlation consistent composite approach, ccCA) for the prediction of classical barrier heights. Modeling the pyrazolate photophysics indicates a significant geometric distortion upon excitation and the impact of both metal identity and substituents on the pyrazolates, pointing to ways in which these systems may be used to produce rationally-tuned phosphors. Similarly, thermodynamic and structural investigations into the catalyst system points to promising candidates for clean catalytic activation of arenes. The ccCA was found to reproduce classical reaction barriers with chemical accuracy, outperforming all DFT, ab initio, and composite methods benchmarked.

Subjects were 2,950 patients who had previously received inpatient treatment for substance abuse at 40 treatment centers in 13 states and were followed up by the Chemical Abuse/Addiction Treatment Outcome Registry (CATOR) via telephone during the 2 years immediately following their treatment. All subjects were contacted every 6 months and asked a series of questions regarding their relapse status, medical utilization, illnesses, injuries, and arrests. Patient status was based on 3 categories: (1) abstinence from any abuse of a chemical, (2) brief relapse of less than 3 months abuse of any chemical, or (3) total relapse of longer than 3 months of any chemical. Findings showed that abstainers had fewer days in the hospital for emotional problems and detoxification. Abstainers also had fewer visits to the hospital for emergency reasons. Males in the brief relapse category had a greater number of injuries than abstainers or total relapsers. Regarding arrests and automobile accidents, no difference was discovered. However, regarding Drunk While Driving (DWI) arrests, abstainers had fewer arrests.

Analzying questioned documents in a nondestructive nature has been an issue for the forensic science community. Using nondestructive techniques such as video spectral comparator does not give reliable information due to the variations in gray or color levels that are distinguished differently by analysts. Destructive techniques such as chromatography give dependable, qualitative and quantitative, information but involves altering the evidentiary value of these questioned documents. The paradox of document examination becomes a problem when document evidence is involved, especially when trying to preserve its evidentiary value and critical data is needed. Thus, a nondestructive technique has been developed to solve the loopholes in document examinations. Direct analyte-probed nanoextraction (DAPNe) is a nanomanipulation technique that extracts ink directly off the document for further examination. A watermark is left, at most, post-extraction. DAPNe utilizes a tip emitter, pre-filled with a solvent, which is controlled in x-, y-, and z-coordinates via joystick controller and aspirates/extracts using a pressure injector. The versatility of this technique lies within the solvent chemistry and its capability to be coupled to various types of instrumentation. The extraction solvent can be altered to target specific components in the ink. For example, a chelator may be added to target metal …

Absence of functional phenylalanine hydroxylase results in phenylketonuria (PKU). Viable treatments remain few, expensive and secondary conditions such as osteopenia occur in most PKU patients. Objective 1: Given the recently described roles of gut microbes to aid host digestion, an orally administered genetically engineered probiotic as the delivery vehicle for enzyme replacement therapy was created. The engineered probiotic, pHENOMMenal, produced phenylalanine ammonia lyase with significant production of trans-cinnamate (phenylalanine cleavage product) in vitro and resulted in a reduction of 515 μM in blood phenylalanine when fed to PKU animals for 14 days (from 2307µM ± 264µM to 1792µM ± 261µM, n = 6, P < 0.05). The control probiotic produced no change in blood phenylalanine. Thus, pHENOMMenal treatment in PKU mice demonstrated engineered microbes could compensate for a metabolic deficiency of the host. Objective 2: Evaluate the PAHenu2 mouse model of PKU for a genetic discrepancy causing ocular enlargement and delayed development observed only after the PAHenu2 mutation was crossed to the C57BL/6J mouse. When compared to healthy littermates, ELISA indicated a consistent but insignificant decrease in plasma IGF-1 and an increase in ocular IGF-1 in PKU animals. SNP screening demonstrated a differential inheritance of IGF-1 alleles in healthy and …

Nucleophiles react with the α-acetoxy derivative of α-hydroxybenzylbenzylnitrosamine at the carbonyl carbon of the acetoxy moiety followed by fragmentation to the very same intermediates formed by oxidative metabolism. Since α-acetoxybenzylbenzylnitrosamine has been shown to be able to acylate nucleophiles and since the nucleic acids are nucleophiles, then it is possible that this compound may cause mutations by an acylation pathway instead of or in addition to the more common alkylation pathway. The data in Part I of this dissertation should be considered in any further biological investigations of N,N-dialkylnitrosamine induced mutagenesis or carcinogenesis. The study of the synthesis, reactions, mutagenicity, and the possible correlation to compound liposolubility of cyclic N-nitrosamines was also investigated.

In recent years scholars have begun to re-evaluate the works, writings, and life of Robert Schumann (1810-1856). One of the primary issues in this ongoing re-evaluation is a reassessment of the composer's late works (roughly defined as those written after 1845). Until recently, the last eight years of Schumann's creative life and the works he composed at that time either have been ignored or critiqued under an image of an illness that had caused periodic breakdowns. Schumann's late works show how his culture and the artists communicating within that culture were transformed from the beginning to the middle of the nineteenth century. These late works, therefore, should be viewed in the context of Schumann's output as a whole and in regard to their contributions to nineteenth-century society. Schumann's contributions, specifically to the genre of the song cycle from 1849 to 1852, are among his late compositional works that still await full reconsideration. A topical study, focusing on three themes of selections from his twenty-three late cycles, will provide a critical evaluation of Schumann's compositional output in the genre of the song cycle. First, Schumann's political voice will be examined. The political events that led to the mid-nineteenth-century revolutions inspired crucial …

In this study, two different field experiments were designed to assess the relative influence of urbanization on benthic communities. During spring and summer, four urban and one reference sites from Denton County, Texas were selected for benthic macroinvertebrate evaluation. Statistically significant differences in colonized benthic macroinvertebrate taxa on artificial substrates were observed among the four urban sites and the reference site. Oligochaetes and chironomids were the dominant taxa at all sites. Identification of chironomid larvae at the subfamily and genus level to detect differences between sites had higher statistical power than the evaluation based on total chironomids. At the reference site, Caenis, Cladotanytarsus, Orthocladius, and Ceratopogonidae were the dominant taxa, while the urban sites were dominated by Dero, Physella, Ancylidae, Chironomus, Dicrotendipes, Glyptotendipes, Polypedilum, Pseudochironomus, Stenochironomus, and Tanytarsus. These differences may have been dependent upon differences in hydrologic regime and water quality between sites. Significant differences (ANOVA, p < 0.01) in water quality parameters (alkalinity, hardness, nitrates, phosphates, chlorides, sulfates, calcium, magnesium, potassium, and triazine) were found among water samples collected from the reference and urban sites. During the transfer period, most of the Ephemeroptera and Trichoptera taxa and a few other taxa disappeared from artificial substrates that were colonized …