Doctor of Philosophy

dissertationThe fundamental interactions between two biologically and environmentally relevant metals, Zn2+ and Cd2+, complexed with water, crown ethers, and histidine are examined using a variety of experimental methods and quantum chemical calculations. Chapters 3 and 6 detail the first experimentally determined hydration energies for n = 6 - 10 for Zn2+(H2O)n and n = 3 - 11 for Cd2+(H2O)n measured using threshold collision-induced dissociation in a guided ion beam mass spectrometer. Kinetic energy dependent cross sections are obtained for each reactant and analyzed to yield 0 K threshold measurements for loss of one, two, and three water ligands after accounting for multiple collisions, kinetic shifts, and energy distributions. The threshold measurements are converted from 0 K to 298 K values to give the hydration enthalpies and free energies for sequentially losing one water from each complex. Theoretical geometry optimizations and single point energy calculations are performed on reactant and product complexes using several levels of theory and basis sets to obtain thermochemistry for comparison to experiment. The charge separation process, M2+(H2O)n - MOH+(H2O)m + H+(H2O)n-m-1, is also observed, analyzed, and discussed in detail in both Chapters 4 and 6 for M = Zn and Cd. In Chapter 5, complexes of Zn2+(H2O)n, where n = 6 - 12, are also examined using infrared multiple photon dissociation (IRMPD) spectroscopy, blackbody infrared radiative dissociation (BIRD), and theory for experimental determination of the coordination behavior of Zn2+. IRMPD spectroscopy experiments and theoretical calculations are also used in Chapter 7 to gain conformational insight into host-guest systems, namely Zn2+ and Cd2+ complexed with crown ethers (12-crown-4, 15-crown-5, and 18-crown-6). Finally, Chapter 8 examines the gas-phase structures of singly and doubly-charged complexes involving Zn and Cd with the amino acid histidine (His) as well as de-protonated His (His-H) using IRMPD spectroscopy

Developing a Just-in-Time Adaptive Mobile Platform for Family Medicine Education: Experiential Lessons Learned

EASEL is a platform designed to provide just-in-time adaptive support to students during experiential learning interviews conducted as part of required work in an online course in a family medicine education program in a Midwestern urban university setting EASEL considers the time and location of the student and provides questions and content before, during, and after the interviews take place EASEL will provide a new way to facilitate and support online family medicine students as they meet with patients and healthcare professionals This paper presents a look at the considerations, issues, and lessons learned during the development process of this interdisciplinary collaborative effort between the platform designers and family medicine faculty while working toward completion of the stud

Threshold collision-induced dissociation of hydrated cadmium (II): experimental and theoretical investigation of the binding energies for Cd2+(H2O)n complexes (n = 4-11)

ManuscriptThe first experimentally determined hydration energies of Cd2+(H2O)n complexes, n = 4 - 11, are measured using threshold collision-induced dissociation in a guided-ion-beam tandem mass spectrometer coupled with an electrospray-ionization source. Kinetic-energy-dependent cross-sections are obtained and analyzed to yield 0 K thresholds for losing one water ligand. The threshold measurements are converted to 298 K values to give the hydration enthalpies and free energies for sequentially losing one water. Trends in these values and calculations at the MP2(full)/SD/6-311+G(2d,2p)//B3LYP /SD/6-311+G(d,p) level are consistent with the inner-solvent shell of Cd2+ being six waters

Sequential bond energies and barrier heights for the water loss and charge separation dissociation pathways of Cd2+(H2O)n, n 3-11

Journal ArticleThe bond dissociation energies for losing one water from Cd2+(H2O)n complexes, n=3?11, are measured using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer coupled with a thermal electrospray ionization source. Kinetic energy dependent cross sections are obtained for n = 4?11 complexes and analyzed to yield 0 K threshold measurements for loss of one, two, and three water ligands after accounting for multiple collisions, kinetic shifts, and energy distributions. The threshold measurements are converted from 0 to 298 K values to give the hydration enthalpies and free energies for sequentially losing one water from each complex. Theoretical geometry optimizations and single point energy calculations are performed on reactant and product complexes using several levels of theory and basis sets to obtain thermochemistry for comparison to experiment. The charge separation process, Cd2+(H2O)n ?CdOH+(H2O)m + H+(H2O)n?m?1, is also observed for n = 4 and 5 and the competition between this process and water loss is analyzed. Rate-limiting transition states for the charge separation process at n = 3?6 are calculated and compared to experimental threshold measurements resulting in the conclusion that the critical size for this dissociation pathway of hydrated cadmium is ncrit = 4

Outdoor music festivals: Cacophonous consumption or melodious moderation?

Large outdoor music festivals have emerged as part of a general expansion of licensed recreational activities, but in research terms they have been largely impenetrable due to commercial sensitivities. These sensitivities notwithstanding, the number and scale of such events necessitate a greater understanding of alcohol and drug use and the potential to promote normative protective behaviours in this context. This study examines self-reported alcohol and drug behaviours of 1589 attendees at a music festival in Scotland during the summer of 2008. Similarities between the outdoor rock music festivals and the dance club scene are considered alongside the challenges associated with risk reduction in these settings. Results show that alcohol was consumed by the majority of samples; however, negative consequences were reported by a minority of respondents, suggesting evidence of controlled hedonism within a situation traditionally associated with unrestrained excess. Similarly, the majority of samples did not use drugs. The majority also report a number of self-regulating protective behaviours suggesting that alcohol and drug use is contained within a developing social culture of ‘controlled intoxication’. Results further suggest that although music festivals are transitory events, there is a degree of consistency amongst attendees. Music festivals may therefore be atypical but potentially effective environments to increase protective behaviours using normative messaging and modern communications media. This study was resourced exclusively by local alcohol and drug partnerships

Emtonjeni—A structural intervention to integrate sexual and reproductive health into public sector HIV care in Cape Town, South Africa: results of a phase II study

Integration of sexual and reproductive health within HIV care services is a promising strategy for increasing access to family planning and STI services and reducing unwanted pregnancies, perinatal HIV transmission and maternal and infant mortality among people living with HIV and their partners. We conducted a Phase II randomized futility trial of a multi-level intervention to increase adherence to safer sex guidelines among those wishing to avoid pregnancy and adherence to safer conception guidelines among those seeking conception in newly-diagnosed HIV-positive persons in four public-sector HIV clinics in Cape Town. Clinics were pair-matched and the two clinics within each pair were randomized to either a three-session provider-delivered enhanced intervention (EI) (onsite contraceptive services and brief milieu intervention for staff) or standard-of-care (SOC) provider-delivered intervention. The futility analysis showed that we cannot rule out the possibility that the EI intervention has a 10 % point or greater success rate in improving adherence to safer sex/safer conception guidelines than does SOC (p = 0.573), indicating that the intervention holds merit, and a larger-scale confirmatory study showing whether the EI is superior to SOC has merit.IS

Developing an Adaptive Mobile Platform in Family Medicine Field Experiences: User Perceptions

EASEL (education through application-supported experiential learning) is a platform designed to provide just-in-time content and reflection opportunities to students during field experiences, such as interviews or field labs, conducted as part of the workload in a course. This study was conducted in area of family medicine education at Indiana University-Purdue University Indianapolis. EASEL allows instructors and students flexibility to engage with course content based on the time of day and the location of each student conducting field work by providing access to questions and content before, during, and after a targeted field experience. In this study, three cohorts of family medicine students (N = 20) interviewed either a health care professional or a patient. Students used EASEL to facilitate and support their experience in the field. This study examined the student perceptions of EASEL. The data indicated instructive information on the usability of the EASEL platform and aided developers in considering future technologies to use as a part of the platform

Anglo American Corporation and the South African state : a contextual analysis of annual reports 1917-1975

Purpose: This paper examines the complex and shifting relationship between the Anglo American Corporation (Anglo) and the South African State (“the State”) as reflected in Anglo’s annual reports. Design/methodology/approach: This paper builds on research on the role of annual reports in ideological conflict. To examine the ongoing relationship between Anglo and the State, we read all the annual reports published by Anglo American from 1917 to 1975, looking for instances in which the corporation appeared to be attempting to address, criticize, compliment, or implore the State. Findings: During the period under study, despite the apparent struggles between the South African State and Anglo American, the relationship between the two was primarily symbiotic. The symbolic confrontation engaged in by these two behemoths perpetuated the real, physical violence perpetrated on the oppressed workers. By appearing to be a liberal opponent of apartheid, Anglo was able to ensure continued investment in South Africa. Social implications: The examination of decades’ worth of annual reports provide an example of how these supposedly neutral instruments were used to contest and sustain power. Thereby, Anglo could continue to exploit workers, reap enormous profits, and maintain a fiction of opposition to the oppressive State. The State also benefited from its support of Anglo, which provided a plurality of tax revenue and economic expansion during the period. Originality/value: This paper provides insights into the ways the State and other institutions sustain each other in the pursuit of economic and political power in the face of visible and widely condemned injustices. Although they frequently contested each other’s primacy, both benefited while black South African miners suffered

Development of a novel ozone- and photo-stable HyPer5 red fluorescent dye for array CGH and microarray gene expression analysis with consistent performance irrespective of environmental conditions

<p>Abstract</p> <p>Background</p> <p>Array-based comparative genomic hybridization (CGH) and gene expression profiling have become vital techniques for identifying molecular defects underlying genetic diseases. Regardless of the microarray platform, cyanine dyes (Cy3 and Cy5) are one of the most widely used fluorescent dye pairs for microarray analysis owing to their brightness and ease of incorporation, enabling high level of assay sensitivity. However, combining both dyes on arrays can become problematic during summer months when ozone levels rise to near 25 parts per billion (ppb). Under such conditions, Cy5 is known to rapidly degrade leading to loss of signal from either "homebrew" or commercial arrays. Cy5 can also suffer disproportionately from dye photobleaching resulting in distortion of (Cy5/Cy3) ratios used in copy number analysis. Our laboratory has been active in fluorescent dye research to find a suitable alternative to Cy5 that is stable to ozone and resistant to photo-bleaching. Here, we report on the development of such a dye, called HyPer5, and describe its' exceptional ozone and photostable properties on microarrays.</p> <p>Results</p> <p>Our results show HyPer5 signal to be stable to high ozone levels. Repeated exposure of mouse arrays hybridized with HyPer5-labeled cDNA to 300 ppb ozone at 5, 10 and 15 minute intervals resulted in no signal loss from the dye. In comparison, Cy5 arrays showed a dramatic 80% decrease in total signal during the same interval. Photobleaching experiments show HyPer5 to be resistant to light induced damage with 3- fold improvement in dye stability over Cy5. In high resolution array CGH experiments, HyPer5 is demonstrated to detect chromosomal aberrations at loci 2p21-16.3 and 15q26.3-26.2 from three patient sample using bacterial artificial chromosome (BAC) arrays. The photostability of HyPer5 is further documented by repeat array scanning without loss of detection. Additionally, HyPer5 arrays are shown to preserve sensitivity and data quality from gene expression experiments.</p> <p>Conclusion</p> <p>HyPer5 is a red fluorescent dye that behaves functionally similar to Cy5 except in stability to ozone and light. HyPer5 is demonstrated to be resistant to ozone at up to 300 ppb, levels significantly higher than commonly observed during summer months. Consequently, HyPer5 dye can be used in parallel with Cy3 under any environmental conditions in array experiments.</p