Computational methods were employed to investigate catalytic processes. First, DFT calculations predicted the important geometry metrics of a copper–nitrene complex. MCSCF calculations supported the open-shell singlet state as the ground state of a monomeric copper nitrene, which was consistent with the diamagnetic character deduced from experimental observations. The calculations predicted an elusive terminal copper nitrene intermediate. Second, DFT methods were carried out to investigate the mechanism of C–F bond activation by a low-coordinate cobalt(I) complex. The computational models suggested that oxidative addition, which is very rare for 3d metals, was preferred. A π–adduct of PhF was predicted to be a plausible intermediate via calculations. Third, DFT calculations were performed to study ancillary ligand effects on C(sp3)–N bond forming reductive elimination from alkylpalladium(II) amido complexes with different phosphine supporting ligands. The dimerization study of alkylpalladium(II) amido complexes indicated an unique arrangement of dative and covalent Pd-N bonds within the core four-membered ring of bimetallic complexes. In conclusion, computational methods enrich the arsenal of methods available to study catalytic processes in conjunction with experiments.

The liberation war was a watershed event in the history of Zimbabwe. According to the ZANU PF (Zimbabwe African National Union Patriotic Front) ruling elites, an understanding of the common experiences of the people during the liberation war provides the best opportunity to mold a common national identity and consciousness. However, the representation of important historical events in a nation's history is problematic. At best events are manipulated for political purposes by the ruling elites, and at the worst they are distorted or exaggerated. In Zimbabwe, the representation of the ZAPU/ZIPRA and the ZANU/ZANLA as liberation movements in high school history textbooks during the armed struggle is a hot potato. This study critically examined and explored the contested "representational practices" of the ZAPU/ZIPRA and the ZANU/ZANLA as liberation movements during the Zimbabwean armed revolution. By means of qualitative content analysis, seven high school history textbooks from Zimbabwe were analyzed. Drawing from postcolonial perspectives and insights, particularly Fanon's concept of the pitfall of national consciousness, the study unveiled the way in which Zimbabwean high school textbooks portrayed the ZAPU/ZIPRA and the ZANU/ZANLA as very different liberation movements whose roles and contributions were unequal. High school textbooks depicted the ZANU/ZANLA as a …

A functional analysis (FA) is the most commonly used assessment methodology for identifying maintaining variables influencing problem behavior. However, if an FA does not produce clear differentiation, researchers and practitioners often then modify procedures to include additional individualized variables. The interview-informed synthesized contingency analysis (IISCA) provides a marked departure from FA methodology and aims to include individualized factors at the initiation of the assessment in order to more rapidly produce differentiation and clear results. We sought to further evaluate and compare the outcomes of two different functional analysis methods: the single-contingency functional analysis (FA) and the interview-informed synthesized contingency analysis (IISCA) to determine the function of problem behavior and evaluate the subsequent function-based treatment determined from the functional analysis results with two children diagnosed with autism spectrum disorder (ASD). Both participants engaged in problem behavior maintained by single-contingencies of reinforcement identified within the single-contingency FA and emphasized by the effectiveness of each single-contingency function-based treatment.

There is a consistent need in many industries, especially oil and gas, to develop coatings which have higher corrosion resistance and better hardness to extend the lifetime of equipment when it is exposed to hostile environments. Electrodeposition has been a favorable method in the synthesis of metal coatings because of its low cost, convenience, ability to work at low temperatures, and ability to control surface morphology and structure. The inclusion of ceramic nanoparticles in metal matrix composites has previously been investigated as a technique to not only increase the corrosion resistance of the native metal but also to improve the hardness and mechanical properties. Cerium oxide nanoparticles were modified through the grafting of organic groups with increasing hydrophobicity for use in nickel coatings on stainless steel to further improve the corrosion properties while maintaining the hardness of the nanocomposite coatings. The process of modifying the cerium oxide nanoparticles involved the use of aryl diazonium salts and resulted in multilayers forming on the surface of the nanoparticles. Praseodymium oxide nanoparticles were also investigated as additives to nickel coatings, since praseodymium oxide has not yet been studied as a possible corrosion protection enhancement in coatings. These coatings were evaluated for composition and …

This research contributes to the cloud computing (CC) literature and information science research by addressing the reality of information sharing and storage behavior (ISSB) of the users' personal information via CC. Gathering information about usage also allows this research to address the paradox between the research and practice. Additionally, this research explores the concept of trust and its role in the behavioral change relative to CC. The findings help reconcile the paradox between the two realms. Essay1 develops and tests cloud computing usage model (CCUM) that assesses ISSB. This model considers the main adoption determinants and the main drawbacks of CC. The study measures the main concerns of users found in the literature, perceived security and perceived privacy. The findings prove surprising on these concerns. Using multiple regression to analyze 129 valid survey responses, the results find that CC users are less concerned about the major issues of security and privacy and will use the technology based on peer usage. Essay 2 examines why users ignore the technology issues and elect to replace the traditional mechanisms for handling their personal information. The results of an interview-based study conducted on 11 normal users and 11 IT professionals clarify their perceptions about …

Marijuana is the second most commonly used substance in the US. A growing literature suggests that socially anxious individuals use marijuana to manage their symptoms in social situations, which may explain why they are also more likely to experience problems. Unfortunately, the majority of the literature is based on research conducted with adult samples or the co-occurrence of diagnoses in adolescent samples. The proposed study sought to test the link between social anxiety (SA) and proxies for ‘real-time' marijuana use behaviors (i.e., use willingness) as well as use-related problems among adolescents. Participants were 69 adolescents (15-17; 55% female) recruited from the community reporting any lifetime marijuana use. Participants were randomly assigned to a novel social rejection or neutral laboratory task and completed measures of SA, marijuana use frequency, and related problems. Consistent with adult findings, main effects of SA and experimental condition on marijuana use willingness were expected to be qualified by an interaction in which the greatest marijuana use willingness would occur among high SA youth post-rejection (H1), SA would be positively related to marijuana use problems (H2), and among adolescents in the rejection condition, marijuana use willingness would be positively correlated with use problems (H3). Only H2 was …

Geckos are famous for the skill of switchable adhesion that they use to stick on various surface while keep their fingers super clean. In the dissertation, a unique mechanism was discovered to explain gecko self-cleaning phenomena. Using atomic force microscopy (AFM), we managed to compare the microparticle-substrate adhesion and the microparticle-seta adhesion with a single seta bonded to the AFM cantilever. A dynamic effect was approved that high pulling-off speed could increase the microparticle-substrate adhesion and thus the self-cleaning appears at high moving speed. Based on the self-cleaning theory, a gecko-inspired N-doped graphene surface with switchable adhesion was achieved, which was designed into a bio-inspired micromanipulator with a success rate over 90%. When electrical bias was applied on this biomimetic surface, the charge concentration induced an electrical double layer (ELD) on the convex surfaces, which attracts polar water molecules to form a water bridge on it, significantly enhancing the adhesion on the wrinkled graphene surface, mimicking the capillary force on beetle feet. Therefore, the bio-inspired adhesive surface can be controlled with speed, electrical bias, humidity and different material surfaces. The water attraction phenomenon on the polarized surface was further tested for the potential application of water collection and evaporation in …

The modern piccolo trumpet is required by professional trumpet players for the performance of solo repertoire, chamber music, orchestra, and wind band. Students in universities around the world study the piccolo trumpet in preparation for professional careers, but relatively few pedagogical tools exist to specifically focus on the nuanced techniques of the instrument such as articulation, range, and sound production. The purpose of this project is to create a pedagogical guide that can serve as a method for students learning the modern piccolo trumpet.

Christopher Rouse (b. 1949), winner of the Pulitzer Prize for his Trombone Concerto (1993) and a Grammy award for his Concerto de Gaudi (1999), has come to the forefront as one of America's most prominent orchestral composers. Several of Rouse's works feature quotations of and strong allusions to other composers' works that are used both rhetorically and structurally. These borrowings range from a variety of different genres and styles of works, from Claudio Monteverdi's L'incoronazione di Poppea to Jay Ferguson's "Thunder Island." Due to the more accessible filtering and funneling methods of musical borrowings (proliferation of mass media), the weighty discourses attached to them, and their variety of functions (critiquing canons, engaging in an allusive tradition, etc.), quotation has become elevated to the most prominent of musical actors that trigger narrative listening strategies, which in turn have a stronger role in the formation of narratives about music as well as narratives of music. The primary aim of this study is to adapt and apply more recent methodological narrativity frameworks to selected instrumental compositions by Rouse containing quotations, suggesting that their manner of insertion, their method of disclosure, and their referential potential can benefit from being examined through various narrative lenses …

Giovanni Legrenzi was a prolific composer of vocal music and maestro di cappella at the Basilica di San Marco but his vocal works are not often studied as a part of the Venetian lineage with composers such as Willaert, de Rore, Zarlino, Monteverdi, Cavalli, and Vivaldi. Despite his being a prolific composer who had significant influence on the work of other musicians in the traditional canon, references to Legrenzi in standard music publications (Grout, Taruskin, Grove Music Online, etc.) are at best sparse, and largely biographical. This dissertation is one step to correct that pattern by creating a performance edition of Sacri e festivi concenti, Opera nona, one of Legrenzi's significant works near the beginning of his Venetian period. This collection of sacred music was published on 12 June 1667 in Venice though Legrenzi's exact whereabouts at the time remain uncertain. This phase of his career can be defined by his having sought more prestigious and lucrative employment. Having lived and worked in rural Lombardy and Ferrara, he made unsuccessful overtures in places such as Milan, Bologna, Vienna, and Paris. A full score has been produced by transcribing from the part books of the Bologna Museo copy, which will allow …

One of the challenges in biology is placing a function on the myriad of gene sequences having become available from rapid advances in genome sequencing. One such example is a gene cluster (Nit1C) found in bacteria that is tied to the unusual ability of certain bacteria to grow when supplied cyanide as the sole nitrogen source. The term cyanotrophs has been applied to such bacteria, for which a genetic linkage between cyanotrophy and Nit1C was demonstrated for 10 separate bacteria. In addition to growth, cyanide induced the expression of Nit1C genes in all organisms tested, and in one case, deletion of one of the Nit1C genes (nitC) caused a loss of growth. Of the ten bacteria able to grow cyanotrophically, all gave evidence of harboring Nit1C on their genome except for two (Pseudomonas fluorescens Pf11764 and P. monteilii BCN3), which were sequenced and the presence of Nit1C was also confirmed. A broader search of bacteria identified 270 separate strains with the cluster, all limited to bacteria spanning the phyla Firmicutes, Actinobacteria, Proteobacteria and Cyanobacteria. Remarkably, many examples of a single representative of a given taxon contained Nit1C, most poignantly displayed by Pf11764 and PmBCN3; the interpretation being the cluster was …

Contemporary repertoire is not commonly taught or explored by teachers during the intermediate level, when a student's musical training is transitioning to an advanced level. Nonetheless, it is important for piano instructors to be open-minded about contemporary music and have some perspective on the development of music repertoire in the future. The purpose of this dissertation is to provide a performance and pedagogical guide to Stephen Chatman's (b. 1950) Fantasies, from both technical and artistic viewpoints. The collection, which consists of eleven pieces, features a wide variety of contemporary idioms, styles, and means of notation. For instance, there are jazz-like syncopated rhythms, asymmetrical accents reminiscent of Primitivism, and Impressionistic or dissonant sonorities. Fantasies is not only a valuable tool for students to explore new sounds and improve their performing techniques while executing nontraditional notations and contemporary idioms, it is also a great teaching resource for instructors to promote students' musicality through hearing, seeing, and thinking. In this study, I provide individual, detailed descriptions for each of the pieces in the score, adding examples on how to address the difficulties they present to the performer. As a result, instructors can better understand how to help students prepare to perform this collection …

This study analyzes the sociocultural factors that affect Saudi students in the U.S. as they seek information and explores to what extent these factors impact their everyday life information seeking (ELIS) behavior and their information technology behavior (ITB). The factors in this study illustrate the unique sociocultural values that distinguish Saudi students from other international student groups: gender segregation, emphasis on religion, social support, and utilization of the consultation concept. After collecting data from an online survey, the data from linear regression analyses revealed that only one culture factor (the language barrier) showed a significant impact on Saudi student ELIS in the U.S., while the other factors were not statistically significant. Also, the findings indicated that perceived usefulness (PU) and perceived ease of use (PEU) were statistically significant to the ELIS of Saudi students. Furthermore, the study showed that after academic information, food and drink, entertainment, and health were the top student needs, the top ranking sources for everyday life seeking information were social media and the Internet. The findings of the study help to shed light on a sizable user group. As the fourth largest group of international students in the U.S., Saudi students have been underrepresented in research. …

Multiple articulation is a technique that is becoming commonplace in the saxophone literature. This study provides a detailed explanation of how produce the technique. Its application to saxophone literature is explored with musical examples and commentary by the author. A compilation of pedagogical viewpoints regarding multiple articulation from educators spanning the last century is provided.

Porphyrins offer a very synthetically flexible template which can be modified in numerous ways to synthesize molecules with very useful properties applicable in areas such as non-linear optical properties, photodynamic therapy, dye-sensitized solar cells, chemical sensors and organic electronic devices. β-Substituted π-extended porphyrins offer unique capabilities in tuning the properties of the molecule towards practical applications. Increased π-conjugation allows the HOMO-LUMO gap to decrease and hence to redshift the absorption into the near-IR region. β-Fused benzoporphyrins offer additional benefits in which the benzene ring itself can be further modified using electron donating substituents and electron donating substituents to electronically tune these porphyrins for various uses. The goal of the research pursued in this dissertation was to develop new methods for the development of β-Substituted π-extended porphyrins and to study their optical and electronic properties. To accomplish this goal, we developed new method to synthesize A2B2 type tetrabenzoporphyrins and we studied the electron transfer in such systems. We also studied the effectiveness of such systems in dye sensitized solar cells. A new method to synthesize functionalized naphthalene fused porphyrins was also developed and we were also able to use this method to synthesize a push-pull naphthalene fused porphyrin.

Through a series of carefully designed experiments, characterization and some modeling tools, this work is aimed at studying the role of thermal profiles on different microstructural zones and associated properties like strength and corrosion through a variation of weld parameters, thermal boundary conditions and material temper. Two different alloys belonging to the Al-Cu and Al-Cu-Li system in different temper conditions- peak aged (T8) and annealed (O) were used. A 3D-thermal pseudo mechanical (TPM) model is developed for the FSW process using heat transfer module in COMSOL Multiphysics and is based on a heat source wherein the temperature dependent yield shear stress is used for the heat generation. The precipitation and coarsening model is based on the Kampmann and Wagner theoretical framework and accounts for the competition between the various nucleation sites for both metastable and equilibrium precipitates. The model predicts different precipitate mean radius and volume fraction for the various zones in the friction stir welded material. A model for the yield strength is developed which considers contributions from different strengthening mechanisms. The predictions of the each models have been verified against experimental data and literature. At constant advance per rotation, the peak temperature decreases with a decrease in traverse …

Poor post-school outcomes for young adults with an autism spectrum disorder (ASD) have underscored the need to gain insight into the use of evidence-based practices (EBPs) in the planning and implementation of transition services. EBPs for effective transition planning and implementation have been documented in the literature but do not appear to be fully utilized in practice to achieve desired student outcomes, reflecting a research-to-practice gap. EBPs have the potential to produce positive outcomes at the high school level, if implemented with fidelity. Special education personnel, especially administrators, play a vital and unique role in transition planning. They can either facilitate or hinder the process. This phenomenological study investigated the perceptions of public school administrators regarding the extent of their awareness of EBPs to ensure the successful transition of students with ASD and associated barriers. Semi-structured interviews were conducted with 10 secondary-level public school administrators. Major themes identified through analyzing the qualitative data included (a) a positive vision for students with ASD, (b) characteristics of a good transition program, (c) administrators' roles in the transition process, (d) barriers to EBP implementation, (e) strategies to reduce barriers, and (f) ownership of what administrators can do to remedy the problem. Lastly, the …

If mania and depression are part of the same pathological processes, one would predict that episodes of one prospectively increase the odds of episodes of the other. The aim of the present study was to test this hypothesis. For comparison purposes, their relationship was contrasted to the relationship between mania and periods of psychosis. Exploratory analyses also tested the degree to which episodes of each occur with greater frequency over time (i.e., kindling). Participants for the present study came from the Suffolk County Mental Health Project (N = 628), a study of first-admission patients with psychosis. Of these participants, 144 met diagnostic criteria for bipolar I disorder and were analyzed for the current study. Results indicated that mania in a given month predicted depression the following month, even after controlling for other symptoms. The reverse, however, was not the case. Mania and psychosis, in contrast, were found to be robust predictors of one another from month to month. Effects were not due to treatment or demographic differences. These findings provide evidence that mania and depression are weakly related. In contrast, mania and psychosis are more closely linked. Findings are consistent with suggestions that psychiatric nosology regroup mania more closely with …

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Positive memories play an important role in the etiology and maintenance of posttraumatic stress disorder (PTSD). Additionally, there are potential clinical benefits of recalling positive memories on affect, cognitions, and behaviors. However, most research/clinical work has focused on the role of traumatic memories in PTSD's symptomatology and treatment. The current study examined positive memory recall difficulties and positive memory phenomenology among 185 trauma-exposed individuals with varying PTSD severity. Participants completed the Life Events Checklist for DSM-5, PTSD Checklist for DSM-5, Autobiographical Memory Test, Memory Experiences Questionnaire – Short Form, Ruminative Thought Style Questionnaire, Difficulties in Emotional Regulation Scale – Brief 16-Item Version, Difficulties in Emotional Regulation Scale – Positive Emotions, the Positive Affect subscale of the Affective Control Scale, and two items from the Pittsburg Sleep Quality Index. Results showed that (1) greater PTSD severity was a marginally significant predictor of fewer recalled positive memories; (2) greater positive emotional dysregulation predicted fewer recalled positive memories controlling for PTSD severity; and (3) increasing PTSD severity predicted more negative valence, less vividness, less coherence, less accessibility, less clear time perspective, fewer sensory details, and greater distancing ratings of the recalled positive memory, controlling for sleep quantity/quality. Such findings add to the PTSD-positive …

This dissertation focuses on the development, characterization, and analysis of luminescent materials and coatings for sensing applications, including CO2, heavy metals, and silver. Chapter 2 involves the use of a gold(I) pyrazolate trimer that is able to detect silver ions with an AgNP medium. Detection of silver is vital, because there is an influx of silver into our environment caused by the increased use of AgNP. Therefore, having a sensor that is able to differentiate between and detect only Ag ions is an important first step to solving the toxicity mystery of AgNPs. Chapter 3 focuses on the development of sensor coatings containing a Eu(III) based luminescent system for sensing dissolved CO2 without the aid of an absorption-based dye. It is well-known that monitoring CO2 levels in our environment is important since even at low concentrations it can cause adverse health effects to the human body. This work demonstrates a pH-sensitive Eu complex being used directly as a CO2 sensor without the aid of any other absorption-based dye. Chapter 4 explores the idea of developing a heavy metal sensor for lead and its ability to detect lead in wide concentration range upon changing the pH of the medium and the …

This work discusses the C-H bond activation by transition metal complexes using various computational methods. First, we performed a DFT study of oxidative addition of methane to Ta(OC2H4)3A (where A may act as an ancillary ligand) to understand how A may affect the propensity of the complex to undergo oxidative addition. Among the A groups studied, they can be a Lewis acid (B or Al), a saturated, electron-precise moiety (CH or SiH), a σ-donor (N), or a σ-donor/π-acid (P). By varying A, we seek to understand how changing the electronic properties of A can affect the kinetics and thermodynamics of methane C–H activation by these complexes. For all A, the TS with H trans to A is favored kinetically over TS with CH3 trans to A. Upon moving from electron-deficient to electron-rich moieties (P and N), the computed C–H activation barrier for the kinetic product decreases significantly. Thus, changing A greatly influences the barrier for methane C–H oxidative addition by these complexes. Secondly, a computational study of oxidative addition (OA) of methane to M(OC2H4)3A (M = Ta, Re and A = ancillary ligand) was carried out using various computational methods. The purpose of this study was to understand how variation …

Internet of Things (IoT) is a promising technology with great potential for individuals, society, governments, and the economy. IoT is expected to become ubiquitous and influence every aspect of everyday experience. Thus, IoT represents an important phenomena for both organizational and behavioral information system (IS) researchers. This dissertation seeks to contribute to IS research by studying the aspects that influence IoT adoption and use at both consumer and organizational levels. This dissertation achieves this purpose in a series of three essays. The first essay focuses on IoT acceptance in the context of smart home. The second essay focuses on examining the effect of artificial intelligence (AI) capabilities on consumers' IoT perceptions and intentions. Finally, the third essay focuses on the organizational investment and adoption of IoT technologies.

This dissertation investigates the interrelationships between a client's non-GAAP earnings disclosures, financial health (profit and loss status), and the external auditor's assessment of the client's going concern status. This dissertation comprises two essays. Essay 1 examines the informativeness and the quality of non-GAAP earnings disclosures in profit and loss firms separately. Using a large sample of non-GAAP earnings voluntarily disclosed by managers, I find that the informativeness and the quality of non-GAAP earnings vary in firms cross-classified by GAAP loss status and non-GAAP loss status. I also find that loss firms have higher quality non-GAAP exclusions relative to profit firms, although the expenses excluded by both profit and loss firms are associated with firms' future performance. Further, I posit and find that profit firms which voluntarily disclose non-GAAP losses have high-quality exclusions, while other non-GAAP reporting profit firms have low-quality exclusions. Having found that non-GAAP earnings in loss firms is opportunistic to some extent, I next study, in Essay 2, whether auditors understand the implications of low-quality non-GAAP reporting in these firms. Specifically, I examine 1) whether non-GAAP earnings disclosures are associated with the propensity of the auditor's going concern issuance to loss firms, and 2) whether non-GAAP earnings disclosures …