The systematic incorporation of Cr ions in a phase-pure silicalite-2 lattice was accomplished through a hydrothermal synthesis using 3,5-dimethylpiperidinium as a templating agent. The chromium ions, after calcination to remove the template, were in the 6+ oxidation state, with their incorporation into the lattice verified by the systematic expansion of the unit cell as a function of Cr loading. The structures of these materials as revealed by electronic spectroscopy and x-ray absorption near-edge spectroscopy (XANES) were consistent with the dioxo-structure typically exhibited by Cr6+ in an amorphous silica matrix. These materials were highly luminescent, with the emission spectra showing an unusually well-resolved vibronic structure characteristic of an emissive site with little in-homogeneous broadening. The site was reduced under flowing CO to Cr4+, as characterized by XANES. The reduction of the Cr from 6+ to 4+ resulted in unit cell volumes that are systematically smaller than those observed with Cr6+, even though the ionic radius of Cr4+ is larger. This is attributed to the fact that the Cr6+ site is not a simple metal ion but a significantly larger [CrO2]2+ unit, requiring a larger lattice expansion to accommodate it. Through analysis of the XANES pre-edge and assignment of the ligand-field spectrum of the Cr4+ ions, it is possible to establish isomorphic substitution into the silicalite lattice Cr6+-silicalite-2 at a low percent Cr loading exhibited a remarkably well resolved vibronic emission which consists of a high frequency progression of 987 cm-1, which is assigned to the fundamental symmetric stretching mode of the (-O-)2Cr(=O)2 groups. A low frequency progression at 214 cm-1, which was assigned to a symmetric O-Cr-O bending mode is built on each band of the 987 cm-1 progression. Studies of the vibronic structure of the emission spectrum as function of temperature and Cr ion concentration reveals an abrupt change in the Franck-Condon factor of the emission at 20 K for sample with very low Cr concentrations (0.03 mol%). The change in the Franck-Condon factor in was attributed to a temperature induced structural change in the coordination sphere of the metal ion. This structural change was found to be accompanied by a concomitant structural change in the lattice structure of the silicalite-2. This structural change, as studied by temperature dependent X-ray diffraction, did not involve a crystallographic phase change but an abrupt decrease in the unit cell volume caused specifically by a decrease in the c axis. This structural change was not observed in pure silicaite-2 indicating that it is not intrinsic to the silicalite lattice. Moreover, no similar structural change is observed at higher Cr loading (> 0.5 mol %). This suggests that the presence of the Cr ions, and the changes in the coordination geometry they undergo at low temperature, induced the observed contraction in the silicalite-2 lattice, in effect acting as a thermal switch that decreases the unit cell volume In spite of its long commercial use, extending over 50 years, the origin of the active sites in the Phillips' ethylene polymerization catalyst (Cr/SiO2) has never been satisfactorily explained. Specifically, what is not fully understood is structure of the organometallic active site that results from initial interactions of the ethylene with the chromium site. Using sol-gel chemistry, the Stiegman's group prepared the Phillip's catalyst as a microporous, optically transparent monolith. These studies have lead to the conclusion that the key organometallic intermediate is a Cr3+ site terminated in an intact vinyl group, Cr3+-CH=CH2.This structure was initially elucidated with solid-state 13C NMR. Further elucidation and confirmation of the presence of the terminal vinyl group was carried out by FT-IR. The spectra collected during the very early stages of polymerization reveals two peaks assignable to the terminal vinyl group. These peaks arise first followed, after several additions of ethylene, by the bands typically assigned to the methylene groups in polyethylene (-CH2-CH2-) which arise from insertion of ethylene between the Cr-vinyl bond. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Fall Semester, 2011. / October 25, 2011. / fluorescence, luminescence, redox active sieves, silicalite, single-site catalysts, vibronic structure / Includes bibliographical references. / Albert E. Stiegman, Professor Directing Dissertation; Peng Xiong, University Representative; Susan Latturner, Committee Member; John Dorsey, Committee Member.

There is a vast literature concerning the political control that elected officials have over agency actors in the development of bureaucratic policymaking outputs. In the context of rulemaking, I theorize that, while political signals play a role in agency response, bureaucratic decision-making is also influenced by agency attention, institutional design and path dependency. Furthermore, I suggest that managers use different strategies in terms of the magnitude and timeliness of their response according to the uncertainty surrounding the aforementioned influences. I use a three-level random intercepts poisson model with quasi-likelihood estimation to analyze an original dataset containing 35 years of rulemaking activity for centralized contracting rules in Florida. I also conduct a qualitative analysis to examine how the nature of rulemaking changes over time. The results suggest that, in addition to political signals, agency attention, path dependency and institutional design also influence bureaucratic response. / A Dissertation submitted to the Askew School of Public Administration and Policy in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Spring Semester, 2012. / March 28, 2012. / bureaucratic response, contracting-out, institutional design, organizational attention, public agency, rulemaking / Includes bibliographical references. / Kaifeng Yang, Professor Directing Dissertation; Christopher Reenock, University Representative; Frances Berry, Committee Member; Ralph Brower, Committee Member; Richard Feiock, Committee Member.

ABSTRACT We calculate the associated production of a pseudoscalar (A) with a pair of heavy quarks at hadonic colliders, namely p pbar, pp →QQA + X for Q = b, t and X the remaining partonic interactions, including one-loop QCD corrections, i.e. at Next-to-leading Order (NLO) in QCD. The one-loop amplitude for the parton level processes q qbar, gg → Q Qbar A is calculated both with a traditional Feynman-diagram approach and with more recently proposed on-shell methods and unitarity based techniques. We use this process as a testing ground to learn and compare the new on-shell methods to more traditional techniques in a case where several massive particles are involved. We present results for the full NLO hadronic cross section, at both the Tevatron (p pbar) and the Large Hadron Collider (pp) with the aim to further aid and constrain the parameter space of models with pseudoscalar production at particle colliders. / A Dissertation submitted to the Department of Physics in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Summer Semester, 2012. / June 29, 2012. / HIGGS, LHC PHYSICS, ON-SHELL METHODS, OPP, QCD, QUANTUM FIELD THEORY / Includes bibliographical references. / Laura Reina, Professor Directing Thesis; Paolo Aluffi, University Representative; Harrison B. Prosper, Committee Member; Takemichi Okui, Committee Member; Simon Capstick, Committee Member.

Background: The cardiovascular (CV) and metabolic health benefits or risks associated with consumption of multi-ingredient performance enhancing supplements (MIPS) in conjunction with periodized resistance training (RT) in resistance trained men are unknown. This population is a major target audience for performance supplements, and therefore, the purpose of this study was to investigate the combined effect of RT and commercially available pre- and post-exercise performance supplements, NO-Shotgun® (SHOT) and NO-Synthesize® (SYN), respectively, on CV risk and body composition in resistance trained men. Methods: Twenty-four resistance trained men completed 6 weeks (3 times/week) of whole-body periodized RT while either ingesting SHOT 30 min pre-exercise and SYN immediately post-exercise or an isocaloric maltodextrin placebo (PL) 30 min pre-exercise and immediately post-exercise. Before and after 6 weeks of RT and supplementation, resting heart rate (HR), blood pressures (BP), total body fat, android fat, gynoid fat, fat-free mass (FFM) and fasting blood measures of glucose, lipids, nitrate/nitrite (NOx), cortisol, and high sensitivity C-reactive protein (CRP) were measured. Statistical analysis was conducted using a 2 x 2 (group x time) repeated measures ANOVA. Significance was set at p<0.05. Results: There was no group x time interaction for HR, BP, blood glucose, lipids, NOx, CRP, cortisol concentrations or body fat. However, there was a time effect where significant decreases in body fat (MIPS: -1.2±1.2%; PL: -0.9±1.1%), android fat (MIPS: -1.8±2.1%; PL: -1.6±2.0%), and gynoid fat (MIPS: -1.3±1.6%; PL: -1.0±1.4%) for both groups were observed. FFM increased in both groups, with MIPS increasing significantly more than the PL group (4.2% vs. 1.9%, p=0.0247). Conclusions: 6 weeks of MIPS ingestion and periodized RT does not alter CV health parameters or blood indices of health or body fat more than a PL treatment in healthy, resistance-trained men. However, MIPS significantly increased FFM. / A Thesis submitted to the Department of Nutrition, Food, and Exercise Sciences in partial fulfillment of the requirements for the degree of Master of Science. / Summer Semester, 2012. / June 19, 2012. / Body Composition, Exercise, Fat-free mass, Resistance Training, Weight lifting, Workout Supplement / Includes bibliographical references. / Michael J. Ormsbee, Professor Directing Thesis; Jeong-Su Kim, Committee Member; Yu Kyoum Kim, Committee Member.

Magnetic materials are used in many applications such as credit cards, hard drives, electric motors, sensors, etc. Although a vast range of magnetic solids is available for these purposes, our ability to improve their efficiency and discover new materials remains paramount to the sustainable progress and economic profitability in many technological areas. The search for magnetic solids with improved performance requires fundamental understanding of correlations between the structural, electronic, and magnetic properties of existing materials, as well as active exploratory synthesis that targets the development of new magnets. Some of the strongest permanent magnets, Nd2Fe14B, SmCo5, and Sm2Co17, combine transition and rare-earth metals, benefiting from the strong exchange between the 4f and 3d magnetic sublattices. Although these materials have been studied in great detail, the development of novel magnets requires thorough investigation of other 3d-4f intermetallics, in order to gain further insights into correlations between their crystal structures and magnetic properties. Among many types of intermetallic materials, ternary pnictides RCo2Pn2 (R = La, Ce, Pr, Nd; Pn = P, As) are of interest because, despite their simple crystal structures, they contain two magnetic sublattices, exchange interactions between which may lead to rich and unprecedented magnetic behavior. Nevertheless, magnetism of these materials was studied only to a limited extent, especially as compared to the extensive studies of their silicide and germanide analogues. The ThCr2Si2 structure type, to which these ternary pnictides belong, is one of the most ubiquitous atomic arrangements encountered among intermetallic compounds. It accounts for over 1000 known intermetallics and has received increased attention due to the recently discovered FeAs-based superconductors. This dissertation is devoted to the investigation of magnetostructural relationships and anomalous magnetic behaviors in rare earth-cobalt pnictides with the ThCr2Si2 structure type, as well as to the development of new synthetic approaches to the preparation of such materials. We use iso- and aliovalent substitutions as effective tools to probe magnetostructural correlations and establish general trends in the magnetic behavior of RCo2Pn2 phases. The modification of the electronic band structure, which correlates with the changes in the crystal structure of the material, is found to act as the driving force that dictates the magnetic properties of these itinerant systems. We demonstrate how this knowledge can be used effectively to achieve diverse magnetic properties and relate them to specific structural characteristics of materials. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Summer Semester, 2012. / June 7, 2012. / Includes bibliographical references. / Michael Shatruk, Professor Directing Dissertation; Theo Siegrist, University Representative; Susan Latturner, Committee Member; Naresh Dalal, Committee Member.

This dissertation is based on an ethnographic study of a living learning community at a large public university in the Southeastern United States. The research was conducted over a four-month period within a program called the Social Justice Living Learning Community (SJLLC), which is sponsored by the Center for Leadership and Civic Education at this institution. The purpose of the study was to gain insight into the relationship between communal and individual beliefs as each is represented through discourse within a community. The study focused on a first-year public speaking course devoted to the values and purpose of the SJLLC. I used ethnographic observation/notes, videotapes of class sessions, recorded interviews that I conducted with leaders and members of the SJLLC, interview data gathered by the Center for Leadership and Civic Education about members' experiences, and drafts of students' speeches to explore this topic. The dissertation focused on the research questions: What is the relationship between a community's core values/beliefs and individual members' textual performances? How do communal values/beliefs constrain and/or enable individual members' production of discourse? My findings demonstrate that communal and individual beliefs interface with one another through ongoing textual performances--texts operating at their highest level of significance--within the SJLLC. Communal beliefs are established through shared communal texts that I classify into three categories: linguistic textual performances, visual textual performances, and participatory textual performances. Linguistic textual performances communicate the SJLLC's belief system, visual textual performances connect students with examples of the belief system through visual media, and participatory textual performances engage students with the belief system through embodied action. The over-arching theme of the community's belief system is a shared belief in positive social change based on A Social Change Model for Leadership Development, Guidebook, Version III. The basic premise of leadership according to the guidebook is that leaders effect positive social change, that positive social change requires collective action, and that a person does not have to hold a "formal position of leadership" to effect such change (16-17). In classroom practices--and in composing their speeches--members of the SJLLC interpret and use this common belief in positive social change for a variety of purposes and in a variety of ways. They re-invent the communal belief and find ways to engage it in connection with their personal beliefs, demonstrating that communal beliefs do enable and engage personal beliefs rather than constricting or silencing them. The study also reveals the reality of tensions that exist between communal and personal beliefs, demonstrating a need for educators to be aware of the challenges students face when negotiating personal beliefs within classroom, professional, and/or societal discourses. Overall, the study demonstrates a need for college educators to develop teaching strategies that allow students to explore the interface of communal and personal beliefs in their lives and as they write in college. / A Dissertation submitted to the Department of English in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Fall Semester, 2011. / October 10, 2011. / belief, community, discourse, ideology, performance, social change / Includes bibliographical references. / Kristie Fleckenstein, Professor Directing Dissertation; Andy Opel, University Representative; Michael Neal, Committee Member; Elaine Treharne, Committee Member.

In this dissertation, I investigate the representations of Saladin in English textual representations from the medieval period to the present, beginning with the romance, King Richard in the fourteenth-century codex, Edinburgh, National Library of Scotland, Advocates 19.2.1, the Auchinleck Manuscript, and continuing to Kingdom of Heaven, a modern Hollywood film. Representations of Saladin are key to helping us understand how the Muslim is characterized in Western popular culture, and how, in contemporary times, those depictions might influence public policy. I argue that American views of Islam are a cultural legacy from Britain due, not only to common language, but also because of the United States' role as a former colony of Great Britain. The representations of Islam as a spiritual and economic threat--through one of its central figures--have a long history and continue to persist because, despite an increasingly global culture, the West has failed to resolve a relationship with Muslim countries that is not dependent upon a binary of superiority and inferiority, of power and opposition. The figure of Saladin has become cultural shorthand in both the East and West for a vision of a region unified by Islam and antagonistic towards the Christian Other. / A Dissertation submitted to the Interdisciplinary Program in the Humanities in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Fall Semester, 2011. / July 5, 2011. / Auchinleck, King Richard, Mark Twain, Piracy, Saladin, Walter Scott / Includes bibliographical references. / Elaine Treharne, Professor Directing Dissertation; Peter Garretson, University Representative; David Johnson, Committee Member; Daniel J. Vitkus, Committee Member.

The perpetration of violent crimes by our youth is a major societal concern and understanding the factors that predispose them to aggressive behavior is of the utmost importance. Therefore, research aimed at identifying risk factors of aggression among high-risk youth are needed for the purpose of informing future intervention strategies. The purpose of the present study was to evaluate cognitive risk factors that have been theorized and shown to play a contributory role in the development of aggression for less severe populations in a sample of male juvenile offenders (N = 119). More specifically, this study investigated the prediction of aggression and related antisocial behavior from youths' self-views (i.e., self-esteem, inflated self-perceptions) and an emotion regulation strategy (i.e., anger rumination) while taking into account personality factors (i.e., narcissism, trait anger) that have also been linked to aggression and share conceptual overlap with these constructs of interest. An evaluation of the psychometric properties of the study measures tapping these constructs provided evidence that these variables could be reliably and validly assessed among a sample of juvenile offenders. Most importantly, anger rumination, anger, self-esteem, and maladaptive narcissism were revealed as significant predictors of juvenile offenders' initial levels of aggression and developmental trajectories of aggression across a four month period. The implications of these findings are discussed. / A Dissertation submitted to the Department of Psychology in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Summer Semester, 2012. / June 18, 2012. / aggresssion, juvenile offenders, risk factors / Includes bibliographical references. / Janet A. Kistner, Professor Directing Dissertation; Kevin Beaver, University Representative; Jeanette Taylor, Committee Member; Joyce Carbonell, Committee Member; Chris Schatschneider, Committee Member.

The growth of a locally isolated strain of green algae, Chlorella sp., selected for its promise as a biodiesel feedstock, was studied in wastewater effluent from the municipal wastewater treatment plant in Tallahassee FL. Nutrient concentration and microbial community composition within the effluent were profiled at monthly intervals. Adequate nutrients for algal cultivation were observed along with a dynamic microbial community of zooplankton, green algae, diatoms, and a bacterial community that included Proteobacteria, Bacteroidetes, Cyanobacteria, Firmicutes, and Actinobacteria. The importance of this microbial community in the cultivation of Chlorella and the impact on biofuel production was investigated utilizing mesocosm incubations. Size exclusion was employed to examine the biogeochemical interactions between the Chlorella culture and the resident wastewater microorganisms. The accumulation of algal cells and chl a biomass, the production of oxygen, and the consumption of inorganic carbon and nutrients, along with changes in the microbial community composition were monitored in treatments that included the total wastewater microbial community, the wastewater bacterial community, and the Chlorella culture with no effluent microorganisms. The treatment that excluded the wastewater microbial community and allowed the Chlorella culture to grow uninfluenced, consistently demonstrated the highest abundances of algal cells. A limited abundance of algal cells and chl a biomass were observed in the treatments that contained the total wastewater microbial community, while no limitation in oxygen production or nutrient consumption was observed in these treatments. Given the presence of zooplankton that are known to graze on algal cells, it appears that a top-down control inhibits the accumulation of algal biomass in raw wastewater effluent from a municipal treatment plant. In the treatments that contained the native bacterial community, competition between the Chlorella culture and phototrophic bacteria, i.e. cyanobacteria, was observed. These treatments demonstrated high chl a biomass, but limited accumulation of algal cells, as well as significant consumption of nutrients, indicating that cyanobacteria may out-compete Chlorella for limiting nutrients. However, the heterotrophic bacterial community did appear to have a significant impact on algal growth. Treatments in which the cyanobacterial community was inhibited did not demonstrate a draw-down of limiting nutrients or a limitation in the accumulation of algal cells. In addition, shifts in the composition of the bacterial community, including a reduction in the relative abundance of Betaproteobacteria with a simultaneous increase in the relative abundance of Alphaproteobacteria, Nostocophycideae, and Oscillatoriophycideae were observed, but these shifts occurred independently of the presence of the Chlorella culture, implying that there is not a strong relationship between these two groups. The limitation that occurred in the growth of Chlorella due to competition and top-down controls indicates that without significant manipulations of the microbial community, the cultivation of an algal monoculture in wastewater effluent from a municipal treatment plant may be unrealistic for efficient biofuel feedstock production. / A Thesis submitted to the Department of Earth, Ocean and Atmospheric Science in partial fulfillment of the requirements for the degree of Master of Science. / Spring Semester, 2012. / April 2, 2012. / Algae, Biofuel, Effluent, Wastewater / Includes bibliographical references. / Jeffrey Chanton, Professor Directing Thesis; Markus Huettel, Committee Member; William Landing, Committee Member; Joel Kostka, Committee Member.

At the outset of career counseling, clarifying the nature of an individual's career problem is vital in order to ascertain the appropriate initial steps of the career intervention (Sampson, Peterson, Reardon, & Lenz, 2000; Spokane, 1991). Identifying and assessing client needs at the beginning of the career service delivery process ensures that services are appropriately aligned with these needs (Gati, Gadassi, Saka, Hadadi, Ansenberg, Friedmann, & Asulin-Peretz, 1996; Sampson et al., 2000; Sampson & Reardon, 1998; Savickas, 1996; Super, 1983). During the initial client assessment it is also important to address mental health issues, as prior research has shown clients having difficulty making career decisions often endorse items such as depression or anxiety (Saunders, Peterson, Sampson, & Reardon, 2000). The Decision Space Worksheet (DSW) is a projective assessment technique that assists clients in understanding the social and emotional context involved in the career decision-making process. In addition, the DSW may also function as a possible indicator of mental health issues out of which a career problem arises (Peterson, Leasure, Carr, & Lenz, 2009). Utilizing the DSW, Career Thoughts Inventory (CTI), and Occupational Alternatives Question (OAQ) at the outset of career counseling could be useful in identifying individuals who are experiencing mental health issues (Lenz, Peterson, Reardon, & Saunders, 2010; Peterson et al., 2009; Walker & Peterson, 2011). This study examines the social and emotional context as portrayed by the DSW in addition to career thoughts and career decidedness as possible indicators of mental health issues in career counseling. Specifically, the question addressed by this study was, "What is the relationship between responses on the DSW and the presence of depressive symptomology?" To answer this question, data were collected for a co-relational study from a sample of 151 enrolled in 8 sections of an undergraduate general psychology course (PSY2012) or psychology of personal and social adjustment course (CLP1001) at a midsized city in a southeastern community college in the United States. No significant positive relationship was found between the DSW total score and the BDI-II score as well as between the respective DSW domains and the BDI-II score. However, there was a contradictory significant inverted relationship between the DSW domain Self-doubt and the BDI-II. Contrary to expectation, Self-doubt statements were negatively associated with depression. The best predictors of depression were found to be the CTI subscales External Conflict (EC) and Commitment Anxiety (CA). There were no significant differences between high and low groups on the BDI-II and DSW responses and no significant differences between the OAQ decided and undecided groups and DSW responses. These findings contribute to the understanding of the DSW's value in assessing the social and emotional context for individuals as they relate to mental health issues, such as depression. Suggestions for modification of the DSW to capture the positive, neutral, or negative value of each statement were provided. The findings of this study implicate other CTI subscales (EC and CA) as significantly capturing unique variation in depression. In addition, these findings support the relationship among the overall CTI and BDI-II scores. Lastly, this study suggests that in non-client populations, who elicit statements on the DSW Self-doubt domain, are less likely to be depressed. Implications for the use of the DSW in non-client populations and recommendations for future research are discussed. / A Dissertation submitted to the Department of Educational Psychology and Learning Systems in partial fulfillment of the requirements for the degree of Doctor of Philosophy. / Fall Semester, 2011. / October 31, 2011. / Career Decision-Making, Career Thoughts Inventory, Decision Space Worksheet, Depression, Mental Health / Includes bibliographical references. / James Sampson, Professor Directing Dissertation; Janet Kistner, University Representative; Gary Peterson, Committee Member; Janet Lenz, Committee Member.