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 the development of extreme North Atlantic cyclones and their relationship with the NAO

The occurrence of extreme cyclones is analysed in terms of their relationship to the NAO phase and the dominating environmental variables controlling their intensification. These are latent energy (equivalent potential temperature 850 hPa is used as an indicator), upper-air baroclinicity, horizontal divergence and jet stream strength. Cyclones over the North Atlantic are identified and tracked using a numerical algorithm, permitting a detailed analysis of their life cycles. Extreme cyclones are selected as the 10% most severe in terms of intensity. Investigations focus on the main strengthening phase of each cyclone. The environmental factors are related to the NAO, which affects the location and orientation of the cyclone tracks, thus explaining why extreme cyclones occur more (less) frequently during strong positive (negative) NAO phases. The enhanced number of extreme cyclones in positive NAO phases can be explained by the larger area with suitable growth conditions, which is better aligned with the cyclone tracks and is associated with increased cyclone life time and intensity. Moreover, strong intensification of cyclones is frequently linked to the occurrence of extreme values of growth factors in the immediate vicinity of the cyclone centre. Similar results are found for ECHAM5/OM1 for present day conditions, demonstrating that relationships between the environment factors and cyclones are also valid in the GCM. For future climate conditions (following the SRES A1B scenario), the results are similar, but a small increase of the frequency of extreme values is detected near the cyclone cores. On the other hand, total cyclone numbers decrease by 10% over the North Atlantic. An exception is the region near the British Isles, which features increased track density and intensity of extreme cyclones irrespective of the NAO phase. These changes are associated with an intensified jet stream close to Europe. Moreover, an enhanced frequency of explosive developments over the British Isles is found, leading to more frequent windstorms affecting Europe.

Factors contributing to the attrition of women in the African-American Nutrition for Life study

Background. There is currently a push to increase the number of minorities in cancer clinical trials in an effort to reduce cancer health disparities. Overcoming barriers to clinical trial research for minorities is necessary if we are to achieve the goals of Healthy People 2010. To understand the unexpectedly high rate of attrition in the A NULIFE study, the research team examined the perceived barriers to participation among minority women. The purpose of this study was to determine if either personal or study-related factors influenced healthy pre-menopausal women aged 25-45 years to terminate their participation in the A NULIFE Study. We hypothesized that personal factors were the driving forces for attrition rates in the prevention trial.^ Methods. The target population consisted of eligible women who consented to the A NULIFE study but withdrew prior to being randomized (N= 46), as well as eligible women who completed the informed consent process for the A NULIFE study and withdrew after randomization (N= 42). Examination of attrition rates in this study occurred at a time point when 10 out of 12 participant groups had completed the A NULIFE study. Data involving the 2 groups that were actively engaged in study activities were not used in this analysis. A survey instrument was designed to query the personal and study-related factors that were believed to have contributed to the decision to terminate participation in the A NULIFE study.^ Results. Overall, the highest ranked personal reason that influenced withdrawal from the study was being “too busy” with other obligations. The second highest ranked factor for withdrawal was work obligations. Whereas, more than half of all participants agreed that they were well-informed about the study and considered the study personnel to be approachable, 54% of participants would have been inclined to remain in the study if it were located at a local community center.^ Conclusions. Time commitment was likely a major factor for withdrawal from the A NULIFE study. Future investigators should implement trials within participant communities where possible. Also, focus group settings may provide detailed insight into factors that contribute to the attrition of minorities in cancer clinical trials.^

Evaluation of the risk factors contributing to the African swine fever occurrence in Sardinia, Italy

This study assesses the relation between hypothesized risk factors and African swine fever virus (ASFV) distribution in Sardinia (Italy) after the beginning of the eradication program in 1993, using a Bayesian multivariable logistic regression mixed model. Results indicate that the probability of ASFV occurrence in Sardinia was associated to particular socio-cultural, productive and economical factors found in the region, particularly to large number of confined (i.e., closed) farms (most of them backyard), high road density, high mean altitude, large number of open fattening farms, and large number of pigs per commune. Conversely, large proportion of open farms with at least one census and large proportion of open farms per commune, were found to be protective factors for ASFV. Results suggest that basic preventive and control strategies, such as yearly census or registration of the pigs per farm and better control of the public lands where pigs are usually raised, together with endanced effords of outreach and communication with pig producers should help in the success of the eradication program for ASF in the Island. Methods and results presented here will inform decision making to better control and eradicate ASF in Sardinia and in all those areas with similar management and epidemiological conditions.

Factors contributing to the differences in peritonitis rates between centers and regions

Despite improvements in connectology, peritoneal dialysis (PD) - associated peritonitis contributes significantly to morbidity and modality failure in patients maintained on PD therapy. A broad spectrum of organisms -gram-positive, gram-negative, fungal, anaerobic - are involved in this complication. In addition, a significant percentage of episodes involve polymicrobial and culture-negative infection. Technological advances are being developed to minimize the incidence of access-related complications such as peritonitis. Many traditional factors such as exit-site infection and poor technique have been already identified. In the present review, we discuss the geographic, patient selection, and clinical issues that can affect peritonitis rates in different areas of the world and in different centers in the same area.

Factors contributing to the retention of seated passengers during emergency stops. Final report.

Urban Mass Transportation Administration, Washington, D.C.

Temporal changes in immigration stress, adaptation, and the factors contributing to the immigration -adaptation process in newly immigrant parents

The adaptation process to a new land can be an arduous transition for families who migrate from their countries in an attempt to evade negative life conditions. Family-based immigration has been the cornerstone of immigration policy for the U.S. However, there has been a relative lack of attention given in immigration studies to the impact of immigration particularly on parents. Furthermore, little is known about their adjustment to their post-migration circumstances, particularly the initial phase of migration, where the psychological impact of immigration tends to be concentrated. It is even rarer that investigators have addressed longitudinally the dynamic process of parents' adaptation to a new ecology, which can shed a great deal of light on its mechanisms. In this dissertation, changes over time in levels of stress, adjustment (affect balance and life satisfaction), and the factors (social support, economic hardship, and discrimination) contributing to stress and adjustment were examined in newly immigrant parents from Argentina, Colombia, Cuba, Haiti, and the West Indies. Moderating effects of gender and country-of-origin were examined as well. This study also aimed to investigate to what extent the contributing factors impacted stress and adjustment, not only concurrently, but also over the first three years of post-migration. Analysis of variance results showed that both affect balance and social support increased whereas life satisfaction decreased over time. There was no significant change in stress, however. Both gender and group effects were also observed. Mothers experienced higher stress whereas fathers experienced higher discrimination. Among groups, Haitians appeared at the greatest risk in terms of stress, discrimination, and economic hardship. A structural equation modeling analysis showed that the relative importance of contributing factors changed over time in the process of immigrants' adaptation. Yet, social support emerged as a powerful protective factor in that its effects carried over time, and discrimination was a primary mediator through which other predictors were related to stress and adjustment. These findings shed light on the "hows and whys" of the immigration-adaptation process, by demonstrating the significance of specific conditions of life change to psychological outcomes as newly immigrant parents adapt to their post-migration ecology.

Factors Contributing to the Academic Performance of BEI Learners

Se analizan los factores que intervienen en el rendimiento académico de los estudiantes del Bachillerato en la Enseñanza del Inglés (BEI) de la Universidad Nacional (Costa Rica). El contexto universitario, el papel de los profesores, la motivación en los estudiantes y los hábitos de estudio son condiciones para fomentar el éxito académico. Según los resultados, los aprendientes necesitan ciertas características personales, motivación y metas para tener éxito en su trabajo académico. Este estudio de caso contribuye a una mejor percepción de los factores que influyen en el mejoramiento de las aptitudes de estudio y aprendizaje, así como los que intervienen en el logro de las metas académicas.This analysis refers to factors contributing to the academic performance of the students majoring in the teaching of English at the Universidad Nacional (Costa Rica). The university context, the professors' role, students' motivation and their study habits are conditions for fostering academic success. The findings indicate that learners need certain personality traits, motivation and goals to succeed in their academic work. This case study provides insight on the factors that influence the enhancement of study skills and leaming, as well as other factors that contribute to the accomplishment of academic goals.

Mechanisms contributing to the enhanced respiratory burst of neutrophils observed in periodontitis

The aim of this thesis is to investigate possible mechanisms that may contribute to neutrophil hyperactivity and hyper-reactivity. One possibility is the presence of a neutrophil priming factors within the peripheral circulation of periodontitis patients. To examine this possibility differentiated HL-60 cells and primary neutrophils were studied in the presence and absence of plasma from periodontitis patients. In independent experiments, plasma was depleted of IL-8, GM-CSF, interferon-a, immunoglobulins and albumin. This work demonstrated that plasma factors such as IL-8, GM-CSF, and interferon-a present during periodontitis may contribute towards the reported hyperactive neutrophil phenotype. Furthermore, this work demonstrated that products from Pg may regulate neutrophil accumulation at infected periodontal sites by promoting gingipain-dependent modification of IL-8-77 into a more biologically active chemokine. To elucidate whether the oxidatively stressed environment that neutrophils are exposed to in periodontitis could influence hyperactivity and hyper-reactivity, neutrophils were depleted of glutathione. This work showed that during oxidative stress, where cellular redox-levels have been altered, neutrophils exhibit an increased respiratory burst. In conclusion, this work highlights the multiple mechanisms that may contribute to neutrophil hyperactivity and hyperreactivity including gingipain-modulated activity of IL-8 variants, the effect of host factors such as IL-8, GM-CSF, interferon-a on neutrophils priming and activation, and the shift of neutrophil GSH:GSSG ratio in favour of a more oxidised environment as observed in periodontitis.

What makes online grocers work? A case study analysis of factors contributing to online grocery store profitability

This research examined the factors contributing to the performance of online grocers prior to, and following, the 2000 dot.com collapse. The primary goals were to assess the relationship between a company’s business model(s) and its performance in the online grocery channel and to determine if there were other company and/or market related factors that could account for company performance. ^ To assess the primary goals, a case based theory building process was utilized. A three-way cross-case analysis comprising Peapod, GroceryWorks, and Tesco examined the common profit components, the structural category (e.g., pure-play, partnership, and hybrid) profit components, and the idiosyncratic profit components related to each specific company. ^ Based on the analysis, it was determined that online grocery store business models could be represented at three distinct, but hierarchically, related levels. The first level was termed the core model and represented the basic profit structure that all online grocers needed in order to conduct operations. The next model level was termed the structural model and represented the profit structure associated with the specific business model configuration (i.e., pure-play, partnership, hybrid). The last model level was termed the augmented model and represented the company’s business model when idiosyncratic profit components were included. In relation to the five company related factors, scalability, rate of expansion, and the automation level were potential candidates for helping to explain online grocer performance. In addition, all the market structure related factors were deemed possible candidates for helping to explain online grocer performance. ^ The study concluded by positing an alternative hypothesis concerning the performance of online grocers. Prior to this study, the prevailing wisdom was that the business models were the primary cause of online grocer performance. However, based on the core model analysis, it was hypothesized that the customer relationship activities (i.e., advertising, promotions, and loyalty program tie-ins) were the real drivers of online grocer performance. ^

What Makes Online Grocers Work? A Case Study Analysis of Factors Contributing to Online Grocery Store Profitability

This research examined the factors contributing to the performance of online grocers prior to, and following, the 2000 dot.com collapse. The primary goals were to assess the relationship between a company’s business model(s) and its performance in the online grocery channel and to determine if there were other company and/or market related factors that could account for company performance. To assess the primary goals, a case based theory building process was utilized. A three-way cross-case analysis comprising Peapod, GroceryWorks, and Tesco examined the common profit components, the structural category (e.g., pure-play, partnership, and hybrid) profit components, and the idiosyncratic profit components related to each specific company. Based on the analysis, it was determined that online grocery store business models could be represented at three distinct, but hierarchically, related levels. The first level was termed the core model and represented the basic profit structure that all online grocers needed in order to conduct operations. The next model level was termed the structural model and represented the profit structure associated with the specific business model configuration (i.e., pure-play, partnership, hybrid). The last model level was termed the augmented model and represented the company’s business model when idiosyncratic profit components were included. In relation to the five company related factors, scalability, rate of expansion, and the automation level were potential candidates for helping to explain online grocer performance. In addition, all the market structure related factors were deemed possible candidates for helping to explain online grocer performance. The study concluded by positing an alternative hypothesis concerning the performance of online grocers. Prior to this study, the prevailing wisdom was that the business models were the primary cause of online grocer performance. However, based on the core model analysis, it was hypothesized that the customer relationship activities (i.e., advertising, promotions, and loyalty program tie-ins) were the real drivers of online grocer performance.

Influence of sugar cane vinasse on the sorption and degradation of herbicides in soil under controlled conditions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)