Factors Affecting Household Disaster Preparedness: A Study of the Canadian Context

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This study addresses the issue of household disaster preparedness. This work contributes two elements to disaster research. The first contribution improve the knowledge of the factors that affect household disaster preparedness. The review of literature yielded three categories of variables that can jointly explain household disaster preparedness: household structure, demographics, and risk-perception factors. In this study 19 variables compose these factors. A second contribution constitutes a theoretical exploration of the concept of disaster preparedness. In this work, four different constructs of disaster preparedness were tested. These constructs include material preparedness, preparedness activities, a combined index, and a weighted and combined index. The study presents the logic and methodology of the index construction and validation. The data used in this study came from households in the Montreal Urban Community (MUC) in Canada. A random sample of 1,003 English- and French-speaking heads of households adequately represents the 1.8 million persons within the MUC. An independent survey firm conducted the interviews in 1996. Results show that the weighted combined household disaster preparedness index constitutes the best construct to represent the concepts under study. Study results also reveal that risk-perception variables (attitudinal factors) offered the strongest explanatory power. Household structure and demographic variables collectively …
Date: December 2000
Creator: Doré, Michel C
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Bird Bones and a Hatched Egg

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A fifty page manuscript of poetry and a critical introduction detailing the poet's aesthetics. Using the idea of the double-image and eroticism, the poet places her work in the category of the surreal. She describes the process of writing poetry born of fragmentary elements as a feminist emergence of agency. The manuscript is composed of four sections, each an element in the inevitable breakdown of a love relationship: meeting, love-making, birth of a child, death. Quotes from various authors of anthropological and fictional texts begin each section to reinforce thematic structure in a process of unveiling the agency of the narrator. The poems are organized as a series, beginning and ending with sequence poems.
Date: December 2000
Creator: Skebe, Carolyn Alifair
Object Type: Thesis or Dissertation
System: The UNT Digital Library

The Effect of Attachment on Preschooler's Emotion Understanding

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The purpose of this study was to identify the relationship between attachment and emotion understanding in preschoolers. Data was collected from 16 preschool children and their mothers recruited from a private learning center in a downtown metropolitan area. Attachment was measured by use of the Attachment Q-sort, 3.0 (Waters, 1995), while emotion understanding was assessed through use of Denham's (1986) affective perspective-taking task and interviews of children concerning naturally occurring emotions and emotion causes (Fabes et al., 1991). Results included a significant correlation (p < .05) between secure attachment and preschooler's ability to decipher the cause of another's emotion; however, a significant correlation was not found between secure attachment and preschooler's perspective-taking ability or ability to name other's emotions. Thus, conclusions about the impact of attachment upon emotion understanding were mixed, and more research on the subject was implicated.
Date: December 2000
Creator: Hernandez, Jennie R.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Logic Programming Tools for Dynamic Content Generation and Internet Data Mining

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The phenomenal growth of Information Technology requires us to elicit, store and maintain huge volumes of data. Analyzing this data for various purposes is becoming increasingly important. Data mining consists of applying data analysis and discovery algorithms that under acceptable computational efficiency limitations, produce a particular enumeration of patterns over the data. We present two techniques based on using Logic programming tools for data mining. Data mining analyzes data by extracting patterns which describe its structure and discovers co-relations in the form of rules. We distinguish analysis methods as visual and non-visual and present one application of each. We explain that our focus on the field of Logic Programming makes some of the very complex tasks related to Web based data mining and dynamic content generation, simple and easy to implement in a uniform framework.
Date: December 2000
Creator: Gupta, Anima
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Behind the Walls: a Guide for Family and Friends of Texas Prison Inmates

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Texas holds one in every nine U.S. inmates. Behind the Walls is a detailed description of one of the world's largest prison systems by a long-time convict trained as an observer and reporter. It spotlights the day-to-day workings of the Texas Department of Criminal Justice-what's good, what's bad, which programs work and which ones do not, and examines if practice really follows official policy. Written to inform about the processes, services, activities, issues, and problems of being incarcerated, this book is invaluable to anyone who has a relative or friend incarcerated in Texas, or for those who want to understand how prisoners live, eat, work, play, and die in a contemporary U.S. prison. Containing a short history of Texas prisons and advice on how to help inmates get out and stay out of prison, this book is the only one of its kind-written by a convict still incarcerated and dedicated to dispelling the ignorance and fear that shroud Texas prisons. Renaud discusses living quarters, food, and clothing, along with how prisoners handle money, mail, visits, and phone calls. He explores the issues of drugs, racism, gangs, and violence as well as what an inmate can learn about his parole, custody …
Date: December 15, 2002
Creator: Renaud, Jorge Antonio
Object Type: Book
System: The UNT Digital Library

Death Lore: Texas Rituals, Superstitions, and Legends of the Hereafter

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Death provides us with some of our very best folklore. Some fear it, some embrace it, and most have pretty firm ideas about what happens when we die. Although some people may not want to talk about dying, it’s the only thing that happens to all of us–and there’s no way to get around it. This Publication of the Texas Folklore Society examines the lore of death and whatever happens afterward. The first chapter examines places where people are buried, either permanently or temporarily. Chapter Two features articles about how people die and the rituals associated with funerals and burials. The third chapter explores some of the stranger stories about what happens after we’re gone, and the last chapter offers some philosophical musings about death in general, as well as our connection to those who have gone before.
Date: December 15, 2008
Creator: Texas Folklore Society
Object Type: Book
System: The UNT Digital Library

Let's Do

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In the nine stories of Let’s Do, various calamities strike ordinary Midwesterners, who cope with a mixture of good intentions and ineptitude. Balancing humor with painful clarity, author Rebecca Meacham pulls readers into the lives of characters who struggle with—and more often against—change. “Rebecca Meacham has one of the freshest voices I've encountered in a long time. Blatantly wise, she creates stories that are deliciously subversive, brave and outrageous, reminiscent of a young Alice Hoffman. As the lives of her characters get derailed, they move with the damaged grace of walking through broken glass on tiptoe. This is a writer whose words speak with emotional resonance about the resilience of the human heart—a beautiful, authentic talent who knows that when you turn life upside down, you get good measures of both trouble and laughter, a lesson the very best writers recognize early.”—Jonis Agee, judge
Date: December 15, 2004
Creator: Meacham, Rebecca
Object Type: Book
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

Sarah T. Hughes: Her Influence in Texas Politics

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Conservative males traditionally dominated Texas politics. In 1930, however, Sarah T. Hughes, a liberal woman from Maryland, began a spectacular career in state politics despite obstacles because of her gender and progressive ideas. First elected to the Texas Legislature in 1930, she remained active in politics for the next fifty years. Hard work, intelligence, and ability allowed her to form solid friendships with Texas's most powerful politicians. She became the first woman in Texas to hold a district judgeship, the first woman from Texas appointed to the federal bench, and the only woman to swear in a U.S. president. Hughes profoundly influenced state politics, challenging the long-standing conservative male domination. She helped to create a more diverse political field that today encompasses different ideologies and both genders.
Date: December 2000
Creator: Justiss, Charnita Spring
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

Work in the calling in Max Weber's Protestant ethic thesis

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Objectives. Scholars have debated Max Weber's theory of the relationship between religion and capitalism for almost 100 years. Still, the debate is clouded by confusion over Weber's claims about religious doctrine and over the supporting evidence. The purpose of this study is to clarify Max Weber's claims regarding the concept of the calling and the related "anti-mammon" injunction and concept of "good works" and substantiate with historical evidence the religious doctrine Weber describes. Methods. Comparative analysis of early Protestant Lutheran and Calvinist documents from the sixteenth and seventeenth centuries was used to flesh out a history of ideas to determine whether evidence exists to support Weber's claims related to religious doctrine. Results. Historical analyses revealed that the concept of the calling pre-dated Luther in the Bible. Luther's innovation was not in his use of the word beruf but in his application of the concept of the calling to the common people and his teaching of that idea. The idea of sanctified work was key in both Lutheran and Calvinist documents. There was an increased emphasis on work and encouragement to accumulate wealth in Calvinist documents. Conclusion. Weber's etymological evidence surrounding Martin Luther's use of the word beruf in his German …
Date: December 2000
Creator: Schindley, Wanda Beatrice Higbee
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Diphosphine Ligand Activation Studies with Organotransition-Metal Compounds

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Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new …
Date: December 2000
Creator: Wang, Jiancheng
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Effects of Reinforcement History on Stimulus Control Relations

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Ray (1969) conducted an experiment on multiple stimulus-response relations and selective attention. Ray's (1969) results suggested that stimulus-response relations function as behavioral units. McIlvane and Dube (1996) indicated that if stimulus-response relations are behavioral units the effects of environmental variables on stimulus-response relations should be similar to the effects of environmental variables on single response topographies. This experiment analyzed the effects of reinforcement history on the probability of stimulus-response relations with differing reinforcement histories. In separate conditions random-ratio schedules of reinforcement were contingent on each of four discriminated responses. To assess the effects of reinforcement, during test conditions stimuli controlling different topographies were present concurrently in composite form. Results show that reinforcement history affects the probability of each response topography and that the association between response topographies and their controlling stimuli tends to remain constant throughout variations in reinforcement probability.
Date: December 2000
Creator: Reyes, Fredy
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Effect of Engineered Surfaces on Valve Performance

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Performance of air operated valves is a major maintenance concern in process industries. Anecdotal information indicates that reliability of some high maintenance valves has been improved by using an ion deposition process to achieve engineered surfaces on selected components. This project compared friction for various surface treatments of selected valve components. Results indicate valve performance may be slightly more consistent when an engineered surface is applied in the valve packing area; however surface treatment in this area does not appear to have a dominant affect on reducing valve friction. Results indicate a linear relation between stem friction and torque applied to packing flange nuts, and even after a valve is in service, controlled packing adjustments can be made without significantly changing valve stroke time.
Date: December 2000
Creator: Pope, Larry G.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Texas Annexation and the Presidential Election of 1844 in the Richmond, Virginia, and New Orleans, Louisiana, Newspaper

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This thesis examines the issue of Texas annexation from the viewpoints of two southern cities: Richmond, Virginia, and New Orleans, Louisiana. It looks primarily at four major newspapers, two in each city: the Richmond Enquirer and the Richmond Whig; and the New Orleans Times-Picayune and the New Orleans Whig. These four newspapers were examined thoroughly from January 1844 to July 1845. In addition to the above newspapers, the Congressional Globe and national voting patterns on Texas annexation were examined. Analysis of the editorial articles in the above newspapers offers the best possibility of understanding public sentiment toward Texas annexation and the presidential election of 1844. The evidence examined in this study indicates that Texas annexation became a decisive issue in the presidential election of 1844. It also shows that, although the press and elements within both Democratic and Whig parties were aware that the slavery question was intricately linked to the Texas annexation issue, slavery and sectional politics were not the primary factors influencing annexation. Ultimately, fundamental concerns regarding western expansion in general, especially for the Whigs, and political party loyalty proved the decisive factors in the presidential election of 1844 and Texas annexation. The evidence gathered in this study …
Date: December 2001
Creator: Short, Steven W.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Characterizaton of Triethoxyfluorosilane and Tetraethoxysilane Based Aerogels

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Aerogels are highly porous, low dielectric constant (low k) materials being considered by the semiconductor industry as an interlayer dielectric. Low k materials are needed to overcome capacitance problems that limit device feature sizes. Precursors triethoxyfluorosilane (TEFS) and tetraethoxysilane (TEOS) were used to prepare bulk aerogels. Samples were prepared by sol-gel methods, and then carbon dioxide supercritically-dried. Effects of varying the water to precursor ratio were studied with respect to aerogel properties and microstructure. Methods of analysis for this study include FTIR-ATR, TEM, RBS, EDS, SEM, dielectric constant determination by impedance and surface area by gas adsorption. Si-F bonds were determined to be present in both acid- and base-catalyzed TEFS as well as HF-catalyzed TEOS. Fluorine promotes a fractal network microstructure as opposed to a particle-like microstructure. Surface area and dielectric constant were determined to increase slightly with increases in the water to precursor ratio.
Date: December 2001
Creator: Roepsch, Jodi Ann
Object Type: Thesis or Dissertation
System: The UNT Digital Library

A meta-analysis of service learning research in middle and high schools.

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This study examines the relationship between service learning innovations and improved academics, self-concept, and social or personal growth in middle and high school students. Meta-Analysis is employed to arrive at effect-size estimates for each construct. A historical overview of service learning is presented and a detailed description of the study selection process is provided. The data revealed a moderate relationship between service learning participation and academics, self-concept and social or personal growth in middle and high school students. The findings are presented, and some appropriate conclusions are drawn. A discussion of the implications of these findings and recommendations for future research are also provided.
Date: December 2001
Creator: White, Amy E.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Immediate and subsequent effects of fixed-time food presentations on automatically maintained mouthing.

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Several studies have demonstrated that fixed-time (FT) schedules of stimulus delivery can function to reduce a variety of behaviors. The purpose of this study was to evaluate the immediate and subsequent effects of FT food deliveries on mouthing. In Phase 1, a preference assessment showed that caramel popcorn, chocolate cookies and pretzels were highly preferred food items. Thus, providing the basis for use of food items during treatment. In Phase 2, a functional analysis showed that mouthing was a nonsocially maintained problem behavior. Phase 3 demonstrated the use of FT schedules of food deliveries as treatment for nonsocially maintained mouthing. Results indicated that FT schedules of food significantly reduced mouthing. In addition, levels of mouthing observed during post-FT observations were reliably lower than pre-FT observations. Treatment effects, operative mechanisms responsible for the treatment effects and the experimental arrangement used to investigate varying FT schedules are discussed.
Date: December 2001
Creator: Simmons, Jason N.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Microwave Cavity Test for Superconductivity

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The first part of this paper describes the Meissner effect in superconductors which serves as the most definitive evidence for superconductivity. It is shown that the microwave perturbation technique may be used to demonstrate this effect. By measuring the changes of resonant frequency and inverse quality factor Q of a microwave cavity with a small volume of sample loading, the Meissner effect can be shown by using the Slater perturbation equation. The experimental system is described with details and the basic principle of each component discussed. The second part of this work describes the technique employed to do the actual measurements. The experiments were conducted on samples of Gallium Arsenide (GaAs) and lead zirconate titanate (PZT) to look for the possible high temperature superconductivity properties. Results of these experiments are presented and discussed. Conclusion and suggestions to future exploration are made.
Date: December 2001
Creator: Tang, Shan
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Teacher Practice, Curriculum, and Children's Moral Development in Buddhist Temple Preschools in Thailand

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This study investigated what constitutes a moral development program in Buddhist temple preschools in Thailand. The researcher employed three qualitative methods: structured, in-depth interviews, observations of teachers' instruction, and document analysis of curriculum guides. Four Buddhist temple preschools were selected as the sites. Participants for interview included three abbots and one head nun, four principals, and twelve teachers. Participants for observations included four teachers of third year classes in each preschool. The study concentrated on four research questions: (a) what are the elements of the character education curriculum? (b) How do teachers teach moral development concepts and skills? (c) What are the teachers' perceptions of the moral development of third year preschoolers? (d) How do teachers assess their pupils' moral development? Key findings for the research questions were: character education was not a subject in the National Preschool Curriculum which was implemented in the Buddhist temple preschools. Core morality was integrated into every topic. The moral behaviors emphasized in the curriculum and the lesson plans included discipline, mindfulness, kindness, helpfulness, patience, honesty, respect, thriftiness, and politeness. The Buddhist concept of the process of moral development includes character education and meditation. The preschoolers were trained to pay respect to teachers and …
Date: December 2001
Creator: Phisalaphong, Rathdow
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Topological uniqueness results for the special linear and other classical Lie Algebras.

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Suppose L is a complete separable metric topological group (ring, field, etc.). L is topologically unique if the Polish topology on L is uniquely determined by its underlying algebraic structure. More specifically, L is topologically unique if an algebraic isomorphism of L with any other complete separable metric topological group (ring, field, etc.) induces a topological isomorphism. A local field is a locally compact topological field with non-discrete topology. The only local fields (up to isomorphism) are the real, complex, and p-adic numbers, finite extensions of the p-adic numbers, and fields of formal power series over finite fields. We establish the topological uniqueness of the special linear Lie algebras over local fields other than the complex numbers (for which this result is not true) in the context of complete separable metric Lie rings. Along the way the topological uniqueness of all local fields other than the field of complex numbers is established, which is derived as a corollary to more general principles which can be applied to a larger class of topological fields. Lastly, also in the context of complete separable metric Lie rings, the topological uniqueness of the special linear Lie algebra over the real division algebra of quaternions, …
Date: December 2001
Creator: Rees, Michael K.
Object Type: Thesis or Dissertation
System: The UNT Digital Library

Comparative Morphology of Sensilla Styloconica on the Proboscis of North American Nymphalidae and Other Selected Taxa: Systematic and Ecological Considerations.

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Sensilla styloconica on the proboscis of 107 species of North American and tropical butterflies were comparatively studied using the scanning electron microscope. Focus was on 76 species of North American Nymphalidae representing 45 genera and 11 subfamilies. Nomenclature for generalized and specific types of nymphalid sensilla is proposed. Written descriptions and micrographs are presented for each species studied. Morphological features were generally consistent for all or most species within genera and sometimes within subfamilies, with specified exceptions. Statistical analysis revealed significant differences for six of eight variables tested between two distinct feeding guilds of North American Nymphalidae. Average number, density, extent of proboscis coverage with sensilla, their total length, and shoulder spine length were all significantly greater in the non-nectar feeding guild than in nectar feeders, and may indicate adaptation for greater efficiency in feeding on flat surfaces. The greater frequency of apical shoulder spines in non-nectar feeders may represent adaptation for protection of sensory pegs from mechanical abrasion during feeding, or for anchoring the flexible proboscis tip to the surface. Correlation analysis revealed 9 out of 28 positive correlations in nectar feeders and 5 out of 28 in non-nectar feeders. Results of preliminary cladistic analysis were not considered to …
Date: December 2001
Creator: Petr, Daniel
Object Type: Thesis or Dissertation
System: The UNT Digital Library

A Novel Phytoestrogen that Acts as an Agonist for Human Estrogen Receptors.

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Estrogen is the natural agonist of the estrogen receptor (ER). However, certain plant-derived compounds or phytoestrogens have been identified that mimic estrogens and act as agonists and/or antagonists of ERs, depending on subtype and target tissue. Understanding how phytoestrogens interact with ERs, and therefore effect the estrogenic response, may prove beneficial in hormone replacement therapy and in the prevention and treatment of hormone-related diseases. Using Thin Layer Chromatography, gas chromatography/mass spectrometry (GC/MS), and proton nuclear nagnetic resonance (HNMR), I identified 4-ethoxymethylphenol (4EM) found in Maclura pomifera. While most phytoestrogens are heterocyclic compounds, 4EM is a simple phenol that acts as an agonist of ER-alpha and -beta in HeLa and MCF-7 cells. To study the effect of 4EM on ER-alpha and -beta activity, I performed transient transfection assays and showed that 4EM activates ER dependent gene transcription in a dose dependent manner in both ER subtypes. Further, 4EM- mediated transcription in ER-alpha, like estrogen, was enhance in the presense of co-activators, SRC-1 (steroid receptor coactivator-1), CBP (CREB binding proteins), and E6-AP (E6-associated protein) and inhibited by trans-4- hydroxytamoxifen (4HT). I found that 4EM was specific for ER and did not activate transcription of the progesterone receptor in HeLa cells.
Date: December 2001
Creator: Pearce, Virginia
Object Type: Thesis or Dissertation
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