The Stabat Mater of Herbert Howells: The Agony and the Ecstasy

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Herbert Howells composed three large works for chorus and orchestra: a requiem (Hymnus Paradisi), Latin mass (Missa Sabrinensis) and finally a Stabat Mater. Writings, performances and recordings of the Stabat Mater, however, have been few. As the Stabat Mater is believed to be the culmination of his musical prowess, it is important to bring this major work to light. Chapter 1 begins with a brief introduction to Herbert Howells, then continues as a brief biographical sketch. Howells's life is discussed from birth, as organ scholar, student at the Royal College of Music, his teaching professorship at the same institution, and important compositions by decade until his death. Chapter 2 is an overview of the Hymnus Paradisi and Missa Sabrinensis. The chapter gives historical information on each work, including reasons for commission, dates of composition and performance, orchestration and choral composition, type of soloists, conductor and recordings. Chapter 3 is an in depth study of the Stabat Mater. The chapter includes reasons for the genesis of the work, current and past events that affected the composition, musical influences, and the death of his son Michael Kendrick Howells. A second section to this chapter addresses the text of the Stabat Mater, including …
Date: August 2006
Creator: Childs, Kim J.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

The Solo Compositions for Trumpet of Fisher Aubrey Tull: An Analysis of Structural, Technical, and Stylistic Elements for Performance Preparation, with Three Recitals of Selected Works by Bozza, Fasch, Haydn, Tomasi, and Others

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The compositions of Fisher Aubrey Tull are widely performed and many have become standard repertoire. Tull's compositions encompass a multiplicity of performance media including works for orchestra, chorus, symphonic band, jazz band, brass choir, and solo and chamber works. Tull's compositional output for the trumpet is prolific and is acknowledged to be music of high quality. An examination of Trumpet and Brass Programs, compiled and published annually by the International Trumpet Guild, shows Tull's solo and ensemble works for trumpet to be frequently performed. Furthermore, his compositions for trumpet have been performed and recorded by internationally acclaimed artists including Vincent DiMartino, Terry Everson, Håkan Hardenberger, Anthony Plog, Carl "Doc" Severinsen and Allen Vizzutti.This study investigates Fisher Tull's eight solo works for trumpet, which include: Vignette for Trumpet and Piano (1954); Concerto No. 1 for Trumpet and Orchestra (1964); Concerto No. 2 for Trumpet and Band (1974); Three Bagatelles for Trumpet and Piano (1975); Eight Profiles for Solo Trumpet (1978); Rhapsody for Trumpet and Band (1980); Sonata for Trumpet and Piano (1986); and Chromutations for Solo Trumpet (1988). Histories of each composition are chronicled. An analysis of formal organization and significant style features examines musical structure, harmonic language, rhythmic character, instrumentation, …
Date: August 2002
Creator: Wenger, Alan J.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Journal of Applied Rehabilitation Counseling, Volume 47, Number 2, Summer 2016

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Official, quarterly journal of the National Rehabilitation Counseling Association (NRCA) containing articles, opinions, and research in professional rehabilitation counseling regarding the needs of individuals employed in a wide variety of work settings and with wide-ranging professional interests.
Date: Summer 2016
Creator: National Rehabilitation Counseling Association (U.S.)
Object Type: Journal/Magazine/Newsletter
System: The UNT Digital Library

'...and one of time.': A Composition for Full Orchestra with Narration

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‘...and one of time.' is a reinterpretation of a small musical moment from Philip Glass' opera, Einstein on the Beach, centered around the phrase "Berne, Switzerland 1905." This reinterpretation is realized through the use of several different compositional techniques including spectral composition, micropolyphony and dodecaphony, as well as the application of extra-musical models developed by Alan Lightman, John Gardner, Italo Calvino and Albert Einstein.
Date: December 1999
Creator: Rinker, John Thomas
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Journal of Applied Rehabilitation Counseling, Volume 44, Number 3, Fall 2013

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Official, quarterly journal of the National Rehabilitation Counseling Association (NRCA) containing articles, opinions, and research in professional rehabilitation counseling regarding the needs of individuals employed in a wide variety of work settings and with wide-ranging professional interests.
Date: September 2013
Creator: National Rehabilitation Counseling Association (U.S.)
Object Type: Journal/Magazine/Newsletter
System: The UNT Digital Library

Peter Lieberson's First Piano Concerto: A Buddhist-inspired poetic vision realized through twelve-tone language, other contemporary compositional techniques, together with three recitals of works by Bach, Chopin, Mozart, Albéniz, Grieg, Ginastera and Paderecki

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The main objective of this document is to explore the life and spiritual convictions of composer Peter Lieberson, and the creation of his Piano Concerto. Lieberson is a sought after composer who has won many awards and commissions. His works have been premiered and performed by some of the best musical artists of the late twentieth- and early twenty-first-century, such as Peter Serkin, Emmanuel Ax, Yo-Yo Ma, and Pierre Boulez. This study is divided into six chapters. After the Introduction, a biographical summary of Peter Lieberson's life, his spiritual beliefs and compositional style is presented. Chapter II contains background information on the Piano Concerto, along with biographical sketches of Peter Serkin, for whom the work was written, and Seiji Ozawa, music director of the Boston Symphony Orchestra and conductor of both the premier performance and Serkin's recording of the piece. Chapter III is a selective survey of the compositional techniques used in Lieberson's Concerto, in terms of the application of twelve-tone theory and the resulting octatonic, pentatonic, and whole-tone scales. Chapter IV introduces a general overview of the influence of Buddhism as a source of inspiration in the Piano Concerto. Chapter V examines aspects of performance practice issues. Chapter VI …
Date: August 2002
Creator: Méndez-Flanigan, Maria Gisela
Object Type: Thesis or Dissertation
System: The UNT Digital Library

The relationship between training in learning style adaptation and successful completion of entry-level community college classes.

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The purpose of this study was to determine if there was a relationship between training in learning style adaptation and successful completion of community college courses. The rationale for conducting this study was based on the need for students to learn how to adapt their learning style in order to more effectively learn in any situation. It is also important that community colleges implement strategies that assist in student retention. The learning styles of entry-level community college students were measured using Kolb's Learning Style Inventory Version 3. Students enrolled in entry-level college courses at a small North Texas community college were studied. The Chi-square Test of Independence with a 2 x 2 design was employed. Findings indicated that there was no statistically significant difference in the relationship between students receiving training in learning styles adaptation and successful completion of entry-level college courses, and that students who attended a learning styles training session and those who did not attend a learning styles training session had an equal chance of succeeding in entry-level community college courses. Findings also indicated that students with Accommodating and Assimilating learning styles are less likely to successfully complete an entry-level college course than are students with Diverging …
Date: December 2002
Creator: Ferrell, Dawn M.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Alternative Information Processing Formats for Overcoming Information Processing Deficits in Senior Adults

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The objective of this study was to examine the effectiveness of alternative advertising presentation formats, and the quantity of information presented in advertisements in overcoming possible information-processing deficits in senior adults that could affect their recall of ad attributes and brand name, the cognitive responses generated, and attitude toward the ad. In addition, the study examined the effectiveness of retirement status as a classification or segmentation variable in comparison with the use of the more traditional classification variable, chronological age. A convenience sample of senior adult volunteers from church groups, social clubs, and civic organizations from the local area were randomly assigned to one of nine experimental conditions. The experiment utilized a simulated magazine to test the effects of presentation formats (3 levels), and quantity of information (3 levels) on senior adult's recall, cognitive responses and attitude toward the test ads. Covariates (gender, wealth, education, activity level, health, and income) were used to reduce variance. The findings clearly indicate that the presentation format of the can ad adversely affected the memory of some senior adults. In addition, the results were significantly different across the different age levels. Retirement status was less beneficial than chronological age in the current study, but …
Date: December 2000
Creator: Muller, Lynn F.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Improving Actigraphy Specificity to Better Inform Insomnia Diagnosis and Treatment Decisions

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Accurate assessment of sleep-wake patterns is important for sleep researchers and clinicians. Actigraphs are low-cost, non-intrusive, wrist-worn activity detectors used to estimate sleep-wake patterns in a natural environment for several nights. Although actigraphy shows good sensitivity (sleep detection), it has consistently demonstrated poor specificity (wakefulness detection while lying in bed relatively motionless). Because insomnia is characterized by wakefulness in bed, actigraphy may not be a valid objective measure of wakefulness for this group. It is possible that refinement of actigraphy software settings for sleep/wake algorithms might improve specificity. The current studies investigated this hypothesis by comparing wake parameters from 48 combinations of actigraphy settings to determine which sleep/wake algorithms best inform insomnia diagnosis and treatment. In the first study, none of the 48 actigraphy setting combinations consistently discriminated between adults with insomnia (n = 69) and non-insomnia (n = 80) on all three wake parameters, and no setting clearly discriminated between groups for the composite variable, total wake time. Similarly, in the second study, no setting combinations consistently discriminated between adults treated for insomnia (n = 18) and controls with untreated insomnia (n = 26) on all three wake parameters. Although two setting combinations discriminated between groups for the composite …
Date: August 2019
Creator: Francetich, Jade Marie
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Construction Applications, Practices, and Techniques of Natural Trumpets: A Comparative Analysis of Baroque and Modern Era Natural Trumpet Construction Methods

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This work discusses in detail the history of, and processes associated with the construction of baroque era trumpets then and now. The work addresses metallurgy, tools, construction methods, and playing characteristics of instruments built with old techniques and modern techniques.
Date: December 2006
Creator: Wells, Lawrence E.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Organizational Change Development Interventions: Are Multiple Interventions Useful?

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The effects of multiple interventions in organizational development change were studied in a comprehensive meta-analytic review. Thirteen organizational interventions were assessed on five outcome variables based upon previous research of six major meta-analytic reviews. Findings based on 138 studies indicated that there were no significant effects of multiple interventions on positive organizational change as opposed to individually implemented interventions. The findings are not congruent with previous findings of organizational development change, and possible issues surrounding these differences are discussed.
Date: August 2005
Creator: Smith, Lindsay C.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Journal of Applied Rehabilitation Counseling, Volume 43, Number 3, Fall 2012

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Official, quarterly journal of the National Rehabilitation Counseling Association (NRCA) containing articles, opinions, and research in professional rehabilitation counseling regarding the needs of individuals employed in a wide variety of work settings and with wide-ranging professional interests.
Date: Autumn 2012
Creator: National Rehabilitation Counseling Association (U.S.)
Object Type: Journal/Magazine/Newsletter
System: The UNT Digital Library

The Ranger Ideal Volume 3: Texas Rangers in the Hall of Fame, 1898–1987

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Established in Waco in 1968, the Texas Ranger Hall of Fame and Museum honors the iconic Texas Rangers, a service that has existed, in one form or another, since 1823. Thirty-one individuals—whose lives span more than two centuries—have been enshrined in the Texas Ranger Hall of Fame. They have become legendary symbols of Texas and the American West. In The Ranger Ideal Volume 3, Darren L. Ivey presents capsule biographies of the twelve inductees who served Texas in the twentieth century. In the first portion of the book, Ivey describes the careers of the “Big Four” Ranger captains—Will L. Wright, Frank Hamer, Tom R. Hickman, and Manuel “Lone Wolf” Gonzaullas—as well as those of Charles E. Miller and Marvin “Red” Burton. Ivey then moves into the mid-century and discusses Robert A. Crowder, John J. Klevenhagen, Clinton T. Peoples, and James E. Riddles. Ivey concludes with Bobby Paul Doherty and Stanley K. Guffey, both of whom gave their lives in the line of duty. Using primary records and reliable secondary sources, and rejecting apocryphal tales, The Ranger Ideal presents the true stories of these intrepid men who enforced the law with gallantry, grit, and guns. This Volume 3 is the finale …
Date: July 2021
Creator: Ivey, Darren L.
Object Type: Book
System: The UNT Digital Library

The Six Piano Sonatas of James Sellars: Aspects of Form, Rhythm, Texture, and Style

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James Sellars has established himself as one of America's foremost composers whose eclectic style reveals a wealth of influences. His artistic combination of various traditional and avant-garde techniques, along with his sensitive and expert craftsmanship has earned him an important position in contemporary American music. Sellars' compositional styles have encompassed neo-Romanticism, in his early days, through post-serialism and Dada to an eclectic, post-Romantic style utilizing popular elements including electro-acoustic techniques. His extensive catalog of over 150 compositions includes works for orchestra, opera, chorus, dance, chamber, voices with ensemble, solo voice, piano, instrumental solos, band, and media. Sellars' compositions for piano solo span a 38-year period and total 17 works, the most important of which are his six one-movement sonatas, which represent, according to Sellars, "a journey from modernism to post-modernism." Their value lies in their eclectic stylistic approaches, artistic nd technical challenges, and pianistic effectiveness. The first three sonatas, incorporating post-serial elements, fall into a modernist stylistic stance while numbers four through six, in postmodern style, contrast one another drastically. Sonata Brasileira, recalls the broad sweeping gestures of the Romantic period; Sonata V reveals the influence of the absurdist Dada movement; and the last sonata Patterns on a Field, blends …
Date: August 2003
Creator: Solomons, John
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Academic Dishonesty: Attitudes and Behaviors of Fundamentalist Christian College Students

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This study was designed to examine: (1) the extent to which cheating occurs in fundamentalist Christian colleges; (2) the attitudes of fundamentalist Christian college students toward cheating; (3) attitudes of fundamentalist Christian college students toward cheating among their peers; (4) the kinds of cheating practices of fundamentalist Christian college students; (5) the degree to which students engage in neutralizing behavior to justify cheating; (6) differences in cheating behaviors according to gender; (7) differences in cheating behaviors according to ethnicity; and (8) differences in cheating behaviors according to the length of duration of Christian commitment. Based upon the responses of 337 students attending 3 different Christian colleges, it was concluded that: (1) most Christian fundamentalist students do not engage in cheating; (2) respondents believe that each of 17 self-reported cheating behaviors are serious forms of cheating; (3) respondents are unlikely to report cheating among peers; (4) plagiarism is the most common cheating behavior; (5) most respondents justify cheating on the basis of the workload at school and the pressure to obtain good grades; (6) there are no differences in cheating behavior according to gender; (7) there are differences in cheating behavior according to groups; and (8) most respondents do not cheat …
Date: December 2000
Creator: Sunday, William G.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Organizational development: A comparison of individual and organizational level change.

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Organizational change and development (OCD) has been studied by researchers to identify the effectiveness of change initiatives. Because of the broad scope of interventions in OCD, these studies have covered a range of areas including multiple interventions and the methodological rigor used by researchers. However, few have looked at organizational versus individual change within an organization, to examine whether individual change is more effective than organizational change. The purpose of this study is to determine if organizational change occurs in a top down or bottom up manner. A meta-analysis was conducted using 238 field experiments. Each study was coded for intervention and organizational outcome and for individual or organizational level variables. Effect sizes were calculated for each study, each level, and each level by intervention and outcome measure. Results indicate that while OCD interventions overall had a moderate effect size, the level of intervention or outcome was not a moderating variable.
Date: August 2005
Creator: Barnett, Michelle L.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

The Crater of Diamonds: A History of the Pike County, Arkansas, Diamond Field, 1906-1972

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The first diamond mine in North America was discovered in 1906 when John W. Huddleston found two diamonds on his farm just south of Murfreesboro in Pike County, Arkansas. Experts soon confirmed that the diamond-bearing formation on which Huddleston made his discovery was the second largest of its kind and represented 25 percent of all known diamond-bearing areas in the world. Discovery of the field generated nearly a half century of speculative activity by men trying to demonstrate and exploit its commercial viability. The field, however, lacked the necessary richness for successful commercial ventures, and mining was eventually replaced in the early 1950s by tourist attractions that operated successfully until 1972. At that time the State of Arkansas purchased the field and converted it to a state park. Thus this work tell the rich and complicated story of America'a once and only diamond field, analyzes the reasons for the repeated failures of efforts to make it commercially viable, and explains how it eventually succeeded as a tourist venture.
Date: May 2002
Creator: Henderson, John C.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Religiousness, current substance use, and early risk indicators for substance abuse and dependence among nursing students.

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The purposes of this study were to examine the prevalence of current substance use and early risk indicators for substance abuse and dependence, and to investigate the relationships among religiousness, current substance use, and early risk indicators among nursing students at seven Seventh-day Adventist colleges. Data for this descriptive study were collected through Efinger's Alcohol Risk Survey (EARS) (Efinger, 1984), the CAGE Questionnaire ( Ewing , 1984), and the Intrinsic/Extrinsic-Revised Scale (Gorsuch & McPherson, 1989). Participants were 241 nursing students enrolled in their first year of nursing courses at seven colleges and universities located across the United States . Findings indicated that 42% of students scored higher than the EARS mean; 24% reported current substance use; and 15% scored in the probable abuse/dependence category of CAGE. Students who reported current substance use and those scoring in the probable substance abuse/dependence category were significantly more likely to score above the EARS median. Intrinsic religiousness demonstrated a significant inverse relationship with current substance use. Significantly lower rates of current substance use were associated with higher rates of attendance at religious services. Respondents who indicated that their religion prohibited alcohol consumption reported significantly lower rates of current substance use than those who answered …
Date: December 2004
Creator: Gnadt, Bonnie
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Depression, Anxiety, Self-Esteem, and Coping in Children and Adolescents Newly Diagnosed with Cancer and Children and Adolescents on Cancer Treatment for a Period of Seven Months or Longer

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Differences in self-reported depression, anxiety, self-esteem, and coping were evaluated in two groups of pediatric oncology patients: newly diagnosed (less than six months post-diagnosis) (n=5) and patients on cancer treatment for seven months or longer (n=5). Participants (6 males, 4 females, ages 7-17 years) completed the Children's Depression Inventory (CDI), the State-Trait Anxiety Inventory for Children (STAIC), and the Culture-Free Self-Esteem Inventory (CFSEI-2); nine of the ten participants discussed in a semi-structured interview their personal experiences and feelings about having cancer. Although the newly diagnosed group had a higher mean score on the CDI than the 7 months or greater group, the difference was not significant (p = .054). The newly diagnosed group also had higher mean state and trait anxiety scores on the STAIC, indicating higher anxiety levels, and a slightly lower CFSEI-2 mean score, indicating slightly lower self-esteem than the 7 months or greater group, but differences were not at a statistically significant level (p>.05).
Date: May 2000
Creator: Jones, Tracy L.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Determination of Dissociation Constants for GABAA Receptor Antagonists using Spontaneously Active Neuronal Networks in vitro

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Changes in spontaneous spike activities recorded from murine frontal cortex networks grown on substrate-integrated microelectrodes were used to determine the dissociation constant (KB) of three GABAA antagonists. Neuronal networks were treated with fixed concentrations of GABAA antagonists and titrated with muscimol, a GABAA receptor agonist. Muscimol decreased spike activity in a concentration dependent manner with full efficacy (100% spike inhibition) and a 50% inhibitory concentration (IC50) of 0.14 ± 0.05 µM (mean ± SD, n=6). At 10, 20, 40 and 80 µM bicuculline, the muscimol IC50 values were shifted to 4.3 ± 1.8 µM (n=6), 6.8 ± 1.7 µM (n=6), 19.3 ± 3.54 µM (n=10) and 43.5 µM (n=2), respectively (mean ± SD). Muscimol titration in the presence of 10, 20, 40 µM of gabazine resulted in IC50s values of 20.1 (n=2), 37.17 (n=4), and 120.45 (n=2), respectively. In the presence of 20, 80, and 160 µM of TMPP (trimethylolpropane phosphate) the IC50s were 0.86 (n=2), 3.07 (n=3), 6.67 (n=2) µM, respectively. Increasing concentrations of GABAA antagonists shifted agonist log concentration-response curves to the right with identical efficacies, indicating direct competition for the GABAA receptor. A Schild plot analysis with linear regression resulted in slopes of 1.18 ± 0.18, 1.29 …
Date: December 2005
Creator: Oli-Rijal, Sabnam
Object Type: Thesis or Dissertation
System: The UNT Digital Library

The Leadership Path of R. Jan LeCroy

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Recent studies reveal that a considerable number of U.S. community college leaders will be retiring in the next several years. The concern is that with the large turnover, history, culture, and important lessons of leadership will be lost. The current research on the lives of presidents, their career paths, and experiences in community college leadership centers on approaches to the study of leadership at the macro level. Limited research exists in the published literature that reports and analyzes the development of individuals as community college leaders at the micro level. This results in a gap regarding understanding leadership development and strategies to prepare leaders. This study addresses this gap by providing a critical description of the leadership development of one individual who became a community college chancellor and who the literature on the community context indicates contributed to the local and national context for community colleges. Biography is gaining prominence as a legitimate and viable tool in the study of leadership. Few biographical studies currently exist which focus on leadership development in context at the micro level. This dissertation is a biographical, qualitative study of the leadership path and legacy of R. Jan LeCroy, a community college leader. The study …
Date: December 2006
Creator: Blankenbaker, Zarina A.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Archive Activism: Memoir of a "Uniquely Nasty" Journey

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Archive Activism is a memoir of activism rooted in a new way to converse with history—by rescuing it. Archive activists discover documents and other important materials often classified, “gone missing,” or sealed that somehow escaped the fireplace or shredder. It is an approach to LGBTQ advocacy and policy activism based on citizen archivery and original archival research to effect social change. Research=Activism is the formula growing out of Charles Francis’s personal story as a gay Texan born and raised during the 1950s and 1960s in Dallas. The rescues range in time and place from Francis’s first encounter with a raucous, near-violent religious demonstration in Fort Worth to attics loaded with forgotten historic treasures of LGBTQ pioneers. Archive Activism tells how Francis helped Governor George W. Bush achieve his dream of becoming president in 2000 by reaching out to gay and lesbian supporters, the first time a Republican candidate for president formally met with gay and lesbian Americans. This inspired Francis to engage with deleted LGBTQ history by forming a historical society with an edge, a new Mattachine Society of Washington, DC. For the first time, Archive Activism reveals how LGBTQ secrets were held for decades at the LBJ Presidential Library …
Date: August 2023
Creator: Francis, Charles C.
Object Type: Book
System: The UNT Digital Library

CEDAR: The Life and Music of Cedar Walton

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Grammy Award–winning pianist, bandleader, and composer Cedar Walton (1934–2013) is a major figure in jazz, associated with a variety of styles from bebop to funk and famous for composing several standards. Born and raised in Dallas, Walton studied music in Denver, where he jammed with musicians such as Charlie Parker and John Coltrane. In 1955, Walton moved to New York, immediately gaining recognition from notable musicians and nightclub proprietors. When Walton returned to the U.S. after serving abroad in the Army, he joined Benny Golson and Art Farmer’s Jazztet. Later, he became both pianist and arranger for Art Blakey’s Jazz Messengers. Next, he worked as part of Prestige Records’s house rhythm section, recording with numerous greats and releasing his own albums. One hallmark of Walton’s impact is his numerous long-term collaborations with giants such as trombonist Curtis Fuller and drummer Billy Higgins. By the end of his career, Walton’s discography, as both band member and bandleader, included many dozens of vaunted recordings with some of the most notable jazz musicians of the 1960s through the first decade of the twenty-first century. Ben Markley conducted more than seventy-five interviews with friends and family members, musicians who played with or were otherwise …
Date: May 2023
Creator: Ben Markley
Object Type: Book
System: The UNT Digital Library

Mechanisms of Methoxide Ion Substitution and Acid- Catalyzed Z/E Isomerization of N-Methoxyimines

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The second order rate constants for nucleophilic substitution by methoxide of (Z)- and (E)-O-methylbenzohydroximoyl fluorides [C6H4C(F)=NOCH3] with various substituents on the phenyl ring [p-OCH3 (1h, 2h), p-CH3 (1g, 2g), p-Cl (1f, 2f), p-H (1e, 2e), (3,5)-bis-CF3 (1i, 2i)] in 90:10 DMSO:MeOH have been measured. A Hammett plot of these rate constants vs σ values gave positive ρ values of 2.95 (Z isomer) and 3.29 (E isomer). Comparison of these rates with methoxide substitution rates for Omethylbenzohydroximoyl bromide [C6H4C(Br)=NOCH3] and Omethylbenzohydroximoyl chloride [C6H4C(Cl)=NOCH3] reveal an element effect for the Z isomers of Br:Cl:F(1e) = 2.21:1.00:79.7 and for the E isomers of Cl:F(2e) = 1.00:18.3. With the p-OCH3-imidoyl halides the following element effects are found: Br:Cl:F(1h) = 2.78:1.00:73.1 for the Z isomer and Br:Cl:F(2h) = 1.97:1.00:12.1 for the E isomer. Measurement of activation parameters revealed ∆S≠ = -17 eu for 1e and ∆S≠ = -9.9 eu for 2e. Ab initio calculations (HF/6-31+G*, MP2/6-31+G*//HF/6-31+G*, B3LYP/6- 31+G*//HF/6-31+G*, HF-SCIPCM/6-31+G*//HF/6-31+G*) were performed to define the reaction surface. These calculations demonstrate a relatively large barrier for nucleophilic attack in relation to halogen loss and support the experimental findings that this reaction proceeds by an addition-elimination mechanism (AN# + DN). The imidoyl fluorides have been used to synthesize …
Date: December 2001
Creator: Dolliver, Debra D.
Object Type: Thesis or Dissertation
System: The UNT Digital Library