Towards reverse engineering of Photosystem II: Synergistic Computational and Experimental Approaches

ABSTRACT Photosystem II (PSII) of oxygenic photosynthesis has the unique ability to photochemically oxidize water, extracting electrons from water to result in the evolution of oxygen gas while depositing these electrons to the rest of the photosynthetic machinery which in turn reduces CO2 to carbohydrate molecules acting as fuel for the cell. Unfortunately, native PSII is unstable and not suitable to be used in industrial applications. Consequently, there is a need to reverse-engineer the water oxidation photochemical reactions of PSII using solution-stable proteins. But what does it take to reverse-engineer PSII’s reactions? PSII has the pigment with the highest oxidation potential in nature known as P680. The high oxidation of P680 is in fact the driving force for water oxidation. P680 is made up of a chlorophyll a dimer embedded inside the relatively hydrophobic transmembrane environment of PSII. In this thesis, the electrostatic factors contributing to the high oxidation potential of P680 are described. PSII oxidizes water in a specialized metal cluster known as the Oxygen Evolving Complex (OEC). The pathways that water can take to enter the relatively hydrophobic region of PSII are described as well. A previous attempt to reverse engineer PSII’s reactions using the protein scaffold of E. coli’s Bacterioferritin (BFR) existed. The oxidation potential of the pigment used for the BFR ‘reaction centre’ was measured and the protein effects calculated in a similar fashion to how P680 potentials were calculated in PSII. The BFR-RC’s pigment oxidation potential was found to be 0.57 V, too low to oxidize water or tyrosine like PSII. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of iii tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. The results were used to develop a second generation of BFR-RC using a high oxidation pigment. The hypervalent phosphorous porphyrin forms a radical pair that can be observed using Transient Electron Paramagnetic Resonance (TR-EPR). Finally, the results from this thesis are discussed in light of the development of solar fuel producing systems.

Factors Contributing to Reading Performance: An In-Depth Analysis of the “Boy Crisis”

This research used a quantitative study approach to investigate the “boy crisis” in Canada. Boy crisis advocates suggest that boys are being surpassed by girls on reading assessments and promote strategies to assist male students. A feminist framework was used in this study that allowed for an investigation and discussion of the factors that mediate between gender and success at reading comprehension, interpretation, and response to text without ignoring female students. Reading scores and questionnaire data compiled by the Pan-Canadian Assessment Program were used in this research, specifically the PCAP-13 2007 assessment of approximately 30,000 13-year-old students from all Canadian provinces and Yukon Territory (CMEC, 2008). Approximately 20,000 participants wrote the reading assessment, while 30,000 students completed the questionnaire responses. Predictor variables were tested using parametric tests such as independent samples t-test, one-way ANOVA, chi-square analysis, and Pearson r. Findings from this study indicate that although boys scored lower than girls on the PCAP-13 2007 reading assessment, factors were found to influence the reading scores of both male and female students to varying degrees. Socioeconomic status, perceptions of the reading material used in language arts classrooms, reading preference, reading interest, parental involvement, parental encouragement for reading, and self-efficacy were all found to affect the reading performance of boys and girls. Relationships between variables were also found and are discussed in this research. The analysis presented in this study allows parents, educators, and policy makers to begin to critically examine and re-evaluate boy crisis literature and offers suggestions on how to improve reading performance for all students of all socioeconomic backgrounds.

For whom the cruiser rolls: a retrospective analysis of factors relating to recidivism in a sample of graduates from a court-ordered alcohol education and awareness program

This study investigated, retrospectively, whether recidivism in a sample of court-ordered'graduates of an alcohol education and awareness program could be predicted. This alcohol education program was based on adult education principles and was philosophically akin to the thoughts of Drs. Jack Mezirow, Stephen Brookfield, and Patricia Cranton. Data on the sample of 214 Halton IDEA (Impaired Driver Education and Awareness) graduates were entered into a spread sheet. Descriptive statistics were generated. Each of the 214 program graduates had taken several tests during the course of the IDEA program. These tests measured knowledge, attitude about impaired driving, and degree of alcohol involvement. Test scores were analyzed to determine whether those IDEA graduates who recidivated differed in any measurable way from those who had no further criminal convictions after a period of at least three years. Their criminal records were obtained from the Canadian Police Information Centre (CPIC). Those program graduates who reoffended were compared to the vast majority who did not reoffend. Results of the study indicated that there was no way to determine who would recidivate from the data that were collected. Further studies could use a qualitative model. Follow-up interviews could be used to determine what impact, if any, attendance at the IDEA program had on the life of the graduates.

A Living Educational Theory of Knowledge Translation: Improving Practice, Influencing Learners, and Contributing to the Professional Knowledge Base

This paper captured our joint journey to create a living educational theory of knowledge translation (KT). The failure to translate research knowledge to practice is identified as a significant issue in the nursing profession. Our research story takes a critical view of KT related to the philosophical inconsistency between what is espoused in the knowledge related to the discipline of nursing and what is done in practice. Our inquiry revealed “us” as “living contradictions” as our practice was not aligned with our values. In this study, we specifically explored our unique personal KT process in order to understand the many challenges and barriers to KT we encountered in our professional practice as nurse educators. Our unique collaborative action research approach involved cycles of action, reflection, and revision which used our values as standards of judgment in an effort to practice authentically. Our data analysis revealed key elements of collaborative reflective dialogue that evoke multiple ways of knowing, inspire authenticity, and improve learning as the basis of improving practice related to KT. We validated our findings through personal and social validation procedures. Our contribution to a culture of inquiry allowed for co-construction of knowledge to reframe our understanding of KT as a holistic, active process which reflects the essence of who we are and what we do.

On the anharmonic, multi-phonon, Debye-Waller contributions to the phonon-limited resistivity of metals : applications to Na and K

The anharmonic, multi-phonon (MP), and Oebye-Waller factor (OW) contributions to the phonon limited resistivity (;0) of metals derived by Shukla and Muller (1979) by the doubletime temperature dependent Green function method have been numerically evaluated for Na and K in the high temperature limit. The anharmonic contributions arise from the cubic and quartic shift of phonons (CS, QS), and phonon width (W) and the interference term (1). The QS, MP and OW contributions to I' are also derived by the matrix element method and the results are in agreement with those of Shukla and Muller (1979). In the high temperature limit, the contributions to;O from each of the above mentioned terms are of the type BT2 For numerical calculations suitable expressions are derived for the anharmonic contributions to ~ in terms of the third and fourth rank tensors obtained by the Ewald procedure. The numerical calculation of the contributions to;O from the OW, MP term and the QS have been done exactly and from the CS, Wand I terms only approximately in the partial and total Einstein approximations (PEA, TEA), using a first principle approach (Shukla and Taylor (1976)). The results obtained indicate that there is a strong pairwise cancellation between the: OW and MP terms, the QS and CS and the Wand I terms. The sum total of these contributions to;O for Na and K amounts to 4 to 11% and 2 to 7%, respectively, in the PEA while in the TEA they amount to 3 to 7% and 1 to 4%, respectively, in the temperature range.

Development of thermally stable versions of the Burgess Reagent : approaches to the chemoenzymatic total synthesis of morphine

The present studies describe our recent work on expanding the use of the Burgess reagent and its reaction with oxiranes. Several new variants of the Burgess reagent and its chiral auxiliary version were evaluated for their thermal stability by NMR spectroscopy. Three new versions of the reagent were synthesized and their stability was determined. The reactivity of all five Burgess reagents was compared in a dehydration reaction and reactions with epoxides and diols. Progress toward a chemoenzymatic synthesis of morphine is also included in this report. The synthesis began with the whole cell oxidation of bromobenzene by Escherichia coli JMI09(pDTG601). The preparation of several precursors for a key step involving the lohnson-Claisen rearrangement and progress toward the total synthesis are described.

Message from the President of the United States, transmitting documents relative to the commencement and progress of any acts or system of retaliation upon prisoners of war, by the Governments of Great Britain and the United States. --

13th Congress, 3d session. House. Doc. no. 13.

Message from the President of the United States, transmitting documents relative to the commencement and progress of any acts or system of retaliation upon prisoners of war, by the Governments of Great Britain and the United States

13th Congress, 3d session. House. Doc. no. 13. October 28, 1814. Read, referred to the Committee on Foreign Relations. Printed by A. and G. Way

Report sent to the President and Director of the Port Dalhousie and Thorold Railway stating that the location of the line extension of the railway is completed

Report sent to the President and Director of the Port Dalhousie and Thorold Railway stating that the location of the line extension of the railway is completed. The distance from Thorold Station to Port Colborne is 20 miles. The estimate provides for construction of a permanent structure across the Chippewa and Welland River. Estimates for building a first class road, culverts and bridges will be of permanent and durable masonry. This includes estimates for various station buildings such as a warehouse in Port Colborne and a warehouse in Port Dalhousie. Surveys and plans are ready and will be registered this week. This is signed by S.D. Woodruff (2 copies) [one appears to be a rough copy] (The rough copy is 5 pages, handwritten and the other copy is 6 pages, handwritten), Apr. 8, 1857.

Letter from S.D. Woodruff to the president and directors of the Port Robinson and Thorold Macadamized Road Committee regarding extra work done

Letter from S.D. Woodruff to the president and directors of the Port Robinson and Thorold Macadamized Road Committee regarding extra work done (3 pages, handwritten), Aug. 6, 1857.

Engineer estimate (5 ½ pages, handwritten) in the marsh lands drainage presented to the Chamber and Councilors of the County of Welland in council assembled

Engineer estimate (5 ½ pages, handwritten) in the marsh lands drainage presented to the Chamber and Councilors of the County of Welland in council assembled. This report is signed by S.D. Woodruff, June 20, 1857.

Bond between Alexander Fraser of the Township of Dumphries to the Honourable William Dickson of Galt

Bond (1 page, printed) between Alexander Fraser of the Township of Dumphries to the Honourable William Dickson of Galt for 304 pounds, June 21, 1830.

Bond between Abram Quackenboss of Dumphries to the Honourable William Dickson of Galt

Bond (1 page, printed) between Abram Quackenboss of Dumphries to the Honourable William Dickson of Galt for 400 pounds, Oct. 27, 1836.