Extracting Ramachandran torsional angle distributions from 2D NMR data using Tikhonov regularization /

Solid state nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for studying structural and dynamical properties of disordered and partially ordered materials, such as glasses, polymers, liquid crystals, and biological materials. In particular, twodimensional( 2D) NMR methods such as ^^C-^^C correlation spectroscopy under the magicangle- spinning (MAS) conditions have been used to measure structural constraints on the secondary structure of proteins and polypeptides. Amyloid fibrils implicated in a broad class of diseases such as Alzheimer's are known to contain a particular repeating structural motif, called a /5-sheet. However, the details of such structures are poorly understood, primarily because the structural constraints extracted from the 2D NMR data in the form of the so-called Ramachandran (backbone torsion) angle distributions, g{^,'4)), are strongly model-dependent. Inverse theory methods are used to extract Ramachandran angle distributions from a set of 2D MAS and constant-time double-quantum-filtered dipolar recoupling (CTDQFD) data. This is a vastly underdetermined problem, and the stability of the inverse mapping is problematic. Tikhonov regularization is a well-known method of improving the stability of the inverse; in this work it is extended to use a new regularization functional based on the Laplacian rather than on the norm of the function itself. In this way, one makes use of the inherently two-dimensional nature of the underlying Ramachandran maps. In addition, a modification of the existing numerical procedure is performed, as appropriate for an underdetermined inverse problem. Stability of the algorithm with respect to the signal-to-noise (S/N) ratio is examined using a simulated data set. The results show excellent convergence to the true angle distribution function g{(j),ii) for the S/N ratio above 100.

Arsenic speciation by ion-exchange chromatography with on- line determination by hydride generation: electronic modification of the D.C. plasma by photon counting

A method using L-cysteine for the determination of arsenous acid (As(III)), arsenic acid (As(V)), monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) by hydride generation was demonstrated. The instrument used was a d.c. plasma atomic emission spectrometer (OCP-AES). Complete recovery was reported for As(III), As(V), and DMAA while 86% recovery was reported for MMAA. Detection limits were determined, as arsenic for the species listed previously, to be 1.2, 0.8, 1.1, and 1.0 ngemL-l, respectively. Precision values, at 50 ngemL-1 arsenic concentration, were f.80/0, 2.50/0, 2.6% and 2.6% relative standard deviation, respectively. The L-cysteine reagent was compared directly with the conventional hydride generation technique which uses a potassium iodide-hydrochloric acid medium. Recoveries using L-cysteine when compared with the conventional method provided the following results: similar recoveries were obtained for As(III), slightly better recoveries were obtained for As(V) and MMAA, and significantly better recoveries for DMAA. In addition, tall and sharp peak shapes were observed for all four species when using L-cysteine. The arsenic speciation method involved separation by ion exchange .. high perfonnance liquid chromatography (HPLC) with on-line hydride generation using the L.. cysteine reagent and measurement byOCP-AES. Total analysis time per sample was 12 min while the time between the start of subsequent runs was approximately 20 min. A binary . gradient elution program, which incorporated the following two eluents: 0.01 and 0.5 mM tri.. sodium citrate both containing 5% methanol (v/v) and both at a pH of approximately 9, was used during the separation by HPLC. Recoveries of the four species which were measured as peak area, and were normalized against As(III), were 880/0, 290/0, and 40% for DMAA, MMAA and As(V), respectively. Resolution factors between adjacent analyte peaks of As(III) and DMAA was 1.1; DMAA and MMAA was 1.3; and MMAA and As(V) was 8.6. During the arsenic speciation study, signals from the d.c. plasma optical system were measured using a new photon-signal integrating device. The_new photon integrator developed and built in this laboratory was based on a previously published design which was further modified to reflect current available hardware. This photon integrator was interfaced to a personal computer through an AID convertor. The .photon integrator has adjustable threshold settings and an adjustable post-gain device.

Rotation-electronic interaction in the 3p-complex Rydberg state of water

An energy theory is formulated for the rotational energy levels in a p-complex Rydberg state of an asymmetric top molecule of symmetry C2v. The effective Hamiltonian used consists of the usual rigid rotor Hamiltonian augmented with terms representing electronic spin and orbital angular momentum effects. Criteria for assigning symmetry species to the rotational energy levels, following Houganfs scheme that uses the full molecular group,are established and given in the form of a table. This is particularly suitable when eigenvectors are calculated on a digital computer. Also, an intensity theory for transitions to the Rydberg p-complex singlet states is presented and selection rules in terms of symmetry species of energy states are established. Finally, applications to HpO and DpO are given.

The electronic spectra and the determination of the excited state geometry of 3A" propynal /|nby Chhiu-Tsu Lin. -- 260 St. Catharines, Ont. : [s. n.],

Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.

Analysis Of The A11a22 X 11a11 And A 33a22 X 1 electronic transitions in selenocarbonyl difluoride

The absorption spectrum of F2CSe in the 18800-21900 cm-1 region has been recorded at -770 C and 220 C under the conditions of medium resolution. The responsible electronic promotion is TI* + n excitation which leads to 3A2 and lA2 excited states. Progressions in vI', v2', v3" v4' and v4" have been identified in the spectrum and have been analyzed in terms of vibronic transitions between a planar ground state and a nQnplanar excited state. The - 3 - 1 - 1 - 1 origins of the a A2 + X Al and A A2 + X Al systems were assigned to the bands at 19018 cm-l and 19689 cm-l . This has given a singlet-triplet splittl. n g lA2 - 3A2 P f 671 cm -1 The out-of-plane wagging levels were found to be anharmonic. 1 -1 Barrier heights of 2483 cm- and 2923 cm were obtained for the lA2 and 3A2 upper states from a fitting of the energy levels of a Lorentzian-quadratic function to the observed levels in the out-of-plane wagging modes. 1 3 For the A2 and A2 states nonplanar equilibrium angles of 30.10 and 31.40 have been evaluated respectively. i

I must walk through the gate : an ontological necessity

This research is a self-study into my life as an athlete, elementary school teacher, leamer, and as a teacher educator/academic. Throughout the inquiry, I explore how my beliefs and values infused my lived experiences and ultimately influenced my constructivist, humanist, and ultimately my holistic teaching and learning practice which at times disrupted the status quo. I have written a collection of narratives (data generation) which embodied my identity as an unintelligent student/leamer, a teacher/learner, an experiential learner, a tenacious participant, and a change agent to name a few. As I unpack my stories and hermeneutically reconstruct their intent, I question their meaning as I explore how I can improve my teaching and learning practice and potentially effect positive change when instructing beginning teacher candidates at a Faculty of Education. At the outset I situate my story and provide the necessary political, social, and cultural background information to ground my research. I follow this with an in depth look at the elements that interconnect the theoretical framework of this self-study by presenting the notion of writing at the boundaries through auto ethnography (Ellis, 2000; Ellis & Bochner, 2004) and writing as a method of inquiry (Richardson, 2000). The emergent themes of experiential learning, identity, and embodied knowing surfaced during the data generation phase. I use the Probyn' s (1990) .. metaphor of locatedness to unpack these themes and ponder the question, Where is experience located? I deepen the exploration by layering Drake's (2007) KnowlDo/Be framework alongside locatedness and offer descriptions of learning moments grounded in pedagogical theories. In the final phase, I introduce thirdspace theory (Bhabha, 1994; Soja, 1996) as a space that allowed me to puzzle educational dilemmas and begin to reconcile the binaries that existed in my life both personally, and professionally. I end where I began by revisiting the questions that drove this study. In addition, Ireflect upon the writing process and the challenges that I encountered while immersed in this approach and contemplate the relevance of conducting a self-study. I leave the reader with what is waiting for me on the other side of the gate, for as Henry James suggested, "Experience is never limited, and it is never complete."

Smart girls : a deconstructive discourse analysis of smartness

This project is a deconstructive discourse analysis of smart girlhood. From a feminist post structural framework, with a focus on discourse and performative identity, I scrutinize three dominant discourses of smartness that are prevalent and academic and popular press. These constructions frame smart girls as being either Losers, Have-It-All Girls, or Imposters. By conducting semi-structured group interviews with six self-identified smart girls, I explore the question of how smart girls perform their smart girl identities in their current sociocultural context. After analyzing the data from the group interviews, I outline five themes that seem to be prevalent in the stories told by the smart girls in this thesis. Finally, I discuss how the performative identities of the smart girls in my thesis appear to be much more complex, multiple and rhizomatic than the discourses under review allow.

Hoosiers on the Hardwood: A Critical Examination of Indiana Basketball Culture and its Effect on Identity Formation

The purpose of this research was to examine the nexus at which Indiana basketball and the state’s ‘hoosier’ identity meet. More specifically, this thesis interrogates the romanticization of this sporting culture for its pedagogical role in the creation of twenty-first century ‘hoosier’ bodies. Adopting a theoretical orientation rooted in critical race theory, I argue that Indiana’s basketball culture represents a normalized / normalizing structure underneath which Otherness is reified to produce hypervisible “different” outsiders (‘non-hoosiers’), and invisible “disciplined” insiders (i.e. ‘hoosiers’). Utilizing data gleaned over a two-month period spent conducting fieldwork in the “hoosier state” (document analysis, unstructured interviewing, and participant observation), I specifically tailor my analysis to uncover people’s understanding, negotiation, and performance of this regional and national subject position. From this point of inquiry, authentic ‘hoosierness’ comes to be represented, known, practiced, and felt in relation to hierarchies of power that privilege white, hypermasculine, rural, and conservative bodies.

Retrospective on the Experience of Parental Pressure and Support by Male Participants that Withdrew from Competitive Youth Hockey: A Phenomenological Investigation

The purpose of this study was to gain an in-depth understanding of the lived experiences of parental pressure and support for males who withdrew from competitive youth hockey. A phenomenological approach was used to explore this phenomenon and develop meaning from the participants' experiences. Data for this study was collected by conducting one in-depth interview with each of the seven participants. Fourteen themes emerged as a result of the data analysis. These themes were grouped into three clusters: (1) Description of parental involvement: “I want them to be there and help me”; (2) Perceived impacts of parental involvement: “I felt like he actually cared”; and (3) Impact of parental involvement on commitment: “I kind of miss hockey now”. The descriptions provided by the participants in this study, and the themes that emerged, offer insight into what it is like for young males to experience parental involvement in competitive youth hockey.

History and Theorizing: The Case of Winemaking in the Ontario Wine Industry

Despite the fact that theorization has been established as an important social mechanism in a variety of contexts, little research has explicated how this process works. I argue that theorization entails strategic constructions of history, or rhetorical history, in order to persuade audiences of legitimacy. I examine the role that history plays in actors’ theorizations of the Ontario wine industry as world class. By conducting a rhetorical analysis of the newsletters and websites of Ontario wineries, I find that various themes of history are routinely employed to re-theorize the industry as one that produces world class wines. In general, the findings suggest that the narratives of Ontario wineries tap into global repertoires of fine wine to portray the continuity of current practices with those of Old World winemaking. In addition, wineries sometimes tap into local histories to convey a sense of uniqueness, but they also obscure the history of poor winemaking in the region.

Exploring the Perceptions of Cultural Competence Among Personal Support Workers in an Ontario Long-Term Care Home: A Case Study

Personal Support Workers (PSWs) spend a large amount of time with long-term care (LTC) home residents providing assistance with their activities of daily living. The s limited research on their perceptions of cultural competence presents the need to bridge this knowledge gap. The researcher conducted a qualitative case study at a LTC home in Ontario. Data were collected by conducting a policy document analysis, a key informant interview with the Director of Care (DOC), and two focus groups with PSWs. The five major overarching themes were: The Culture of the LTC Home, Provision of a Supportive Environment, Collaborative Team Approach to Care, Building a Relationship with the Residents, and Maintenance of Staff Morale. The findings illuminated the broad nature of culture, connections to person centered care, and the factors that facilitate or hinder PSWs’ culturally competent care. The ambiguous perception of cultural competence among PSWs suggests further research and education on cultural competence in LTC home settings.

Understanding Continuance Intentions of Physicians with Electronic Medical Records (EMRS): An Expectancy-Confirmation Perspective

This thesis examines physicians’ satisfaction with electronic medical records (EMRs) in the post-adoption phase. More specifically, the study examines how physicians’ satisfaction with EMRs impacts on their intention to continue using as well as extend their adoption of additional functions of EMRs. Expectation-confirmation theory is used with the incorporation of perceived risk as the theoretical framework. The extended theoretical model is used to formulate eight hypotheses to aid in the understanding of physicians’ continuance intentions. A field survey of 135 Canadian physicians that utilize EMRs was performed to test the model empirically. The study found that physicians are willing to continue using and adopting additional components of EMRs. In addition, the empirical results suggest that physicians’ perceived usefulness and perceived risk impacts satisfaction, which in turn influences physicians’ continuance intentions. As well, perceived risk has an influence on physicians’ continuance intentions directly.

Developing an Understanding of Cultural Diversity: How an Experience Living in a Multicultural Nation and an Experience Teaching Abroad Contribute to Southern Ontario Teachers' Identities

This is a narrative design study focusing on the understandings that a group of 6 Southern Ontario teachers have of cultural diversity and how these understandings integrated into their development of teacher identity. Given the high culturally diverse population of Canada and its national multicultural values, conducting this study on Canadian pre-service and in-service teachers offers an interesting contribution to the field. In efforts to explore the participants’ understandings, the research examined a teaching abroad experience. The aim was to investigate how these participants gained insight from their experiences with cultural diversity and whether these insights stimulated a greater culturally conscious teacher identity. Narratives provided a description of the lived experiences of these 6 teachers and identified meanings made from these experiences. Participants included 2 pre-service teachers who were in a teacher education program at the time of the interview, and 4 certified teachers who graduated from a teacher education program within the past 5 years. One on one interviews focused on lived experiences within a participant’s home, school community, and teaching abroad. The researcher used grounded theory during the data analysis to assist in identifying themes, and then compared these themes among participants. Overall, this study suggests that even though these participants live in a multicultural nation, experiences varied greatly based on contributing factors such as heritage and exposure to cultural diversity through their home and school life. Despite their varying level of cultural competence, all participants gained insight from their teaching abroad experience, contributing to a teacher identity that considered inclusive practices. This study suggests that there are some important factors to consider when preparing teachers to teach in a multicultural society.

BP BLOGGER: DESCRIPTIVE STUDY OF ELECTRONIC KNOWLEDGE DISSEMINATION IN LONG TERM CARE

Little is known of the uptake and use of knowledge disseminated in electronic formats, especially in Long Term Care (LTC) settings. The purpose of this descriptive study was to examine the dissemination of the BP Bloggers, a series of brief, evidence summaries designed to meet the knowledge needs of LTC staff. Guided by Rogers’ (2003) Diffusion of Innovations theory, the study documents dissemination of the BP Blogger and examines factors affecting dissemination, awareness, perceptions and its use. The survey of BP Blogger recipients was conducted electronically (n=114) online (n=10), by telephone (n=55), and print (n=144). Managers usually received the newsletter electronically while staff in LTC were more likely to receive printed copies. Participants disseminated the newsletter through paper, email, or posting in the workplace. Most participants rated the content, format, and usefulness of the BP Blogger as good or excellent. Time and lack of email access were barriers to dissemination.

THE ASSOCIATION OF SEQUENCE OF HIRING PRACTICE AND BIOPHYSICAL COMPONENTS IN SCREENING PROBATIONARY FIREFIGHTERS

Variation in hiring procedures occurs within fire service human resource departments. In this study, City 1 and City 2 applicants were required to pass their biophysical assessments prior to being hired as firefighters at the beginning and end of the screening process, respectively. City 1 applicants demonstrated significantly lower resting heart rate (RHR), resting diastolic blood pressure (RDBP), body fat% (BF) and higher z-scores for BF, trunk flexibility (TF) and overall clinical assessment (p<0.05). Regression analysis found that age and conducting the biophysical assessment at the end of the screening process explained poorer biophysical assessment results in BF% (R2=21%), BF z-score (R2=22%), TF z-score (R2=10%) and overall clinical assessment z-score (R2=7%). Each of RHR (OR=1.06, CI=1.01-1.10), RDBP (OR=1.05, CI=1.00-1.11) and BF% (OR=1.20, CI=1.07-1.37) increased the odds of being a City 2 firefighter (p<0.05). Biophysical screening at the end of the hiring process may result in the hiring of a less healthy firefighter.