Chlorine contribution to quantitative structure and activity relationship models of disinfection by -products' quantum chemical descriptors and toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: (1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (E LUMO) via QSAR modelling and analysis; (2) to validate the models by using internal and external cross-validation techniques; (3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl ) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: (1) Linear or Multi-linear Regression (MLR); (2) Partial Least Squares (PLS); and (3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: (1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; (2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; (3) E LUMO are shown to correlate highly with the NCl for several classes of DBPs; and (4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Chlorine Contribution to Quantitative Structure and Activity Relationship Models of Disinfection By-Products' Quantum Chemical Descriptors and Toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: 1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (ELUMO) via QSAR modelling and analysis; 2) to validate the models by using internal and external cross-validation techniques; 3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: 1) Linear or Multi-linear Regression (MLR); 2) Partial Least Squares (PLS); and 3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: 1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; 2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; 3) ELUMO are shown to correlate highly with the NCl for several classes of DBPs; and 4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Tailoring heme -thiolate proteins into efficient biocatalysts with high specificity and selectivity

Cytochrome P450 monooxygenases, one of the most important classes of heme-thiolate proteins, have attracted considerable interest in the biochemical community because of its catalytic versatility, substrate diversity and great number in the superfamily. Although P450s are capable of catalyzing numerous difficult oxidation reactions, the relatively low stability, low turnover rates and the need of electron-donating cofactors have limited their practical biotechnological and pharmaceutical applications as isolated enzymes. The goal of this study is to tailor such heme-thiolate proteins into efficient biocatalysts with high specificity and selectivity by protein engineering and to better understand the structure-function relationship in cytochromes P450. In the effort to engineer P450cam, the prototype member of the P450 superfamily, into an efficient peroxygenase that utilizes hydrogen peroxide via the “peroxide-shunt” pathway, site-directed mutagenesis has been used to elucidate the critical roles of hydrophobic residues in the active site. Various biophysical, biochemical and spectroscopic techniques have been utilized to investigate the wild-type and mutant proteins. Three important P450cam variants were obtained showing distinct structural and functional features. In P450camV247H mutant, which exhibited almost identical spectral properties with the wild-type, it is demonstrated that a single amino acid switch turned the monooxygenase into an efficient preoxidase by increasing the peroxidase activity nearly one thousand folds. In order to tune the distal pocket of P450cam with polar residues, Leu 246 was replaced with a basic residue, lysine, resulting in a mutant with spectral features identical to P420, the inactive species of P450. But this inactive-species-like mutant showed catalytic activities without the facilitation of any cofactors. By substituting Gly 248 with a histidine, a novel Cys-Fe-His ligation set was obtained in P450cam which represented the very rare case of His ligation in heme-thiolate proteins. In addition to serving as a convenient model for hemoprotein structural studies, the G248H mutant also provided evidence about the nature of the axial ligand in cytochrome P420 and other engineered hemoproteins with thiolate ligations. Furthermore, attempts have been made to replace the proximal ligand in sperm whale myoglobin to construct a heme-thiolate protein model by mimicking the protein environment of cytochrome P450cam and chloroperoxidase.

Tailoring Heme-Thiolate Proteins into Efficient Biocatalysts with High Specificity and Selectivity

Cytochrome P450 monooxygenases, one of the most important classes of heme-thiolate proteins, have attracted considerable interest in the biochemical community because of its catalytic versatility, substrate diversity and great number in the superfamily. Although P450s are capable of catalyzing numerous difficult oxidation reactions, the relatively low stability, low turnover rates and the need of electron-donating cofactors have limited their practical biotechnological and pharmaceutical applications as isolated enzymes. The goal of this study is to tailor such heme-thiolate proteins into efficient biocatalysts with high specificity and selectivity by protein engineering and to better understand the structure-function relationship in cytochromes P450. In the effort to engineer P450cam, the prototype member of the P450 superfamily, into an efficient peroxygenase that utilizes hydrogen peroxide via the “peroxide-shunt” pathway, site-directed mutagenesis has been used to elucidate the critical roles of hydrophobic residues in the active site. Various biophysical, biochemical and spectroscopic techniques have been utilized to investigate the wild-type and mutant proteins. Three important P450cam variants were obtained showing distinct structural and functional features. In P450camV247H mutant, which exhibited almost identical spectral properties with the wild-type, it is demonstrated that a single amino acid switch turned the monooxygenase into an efficient preoxidase by increasing the peroxidase activity nearly one thousand folds. In order to tune the distal pocket of P450cam with polar residues, Leu 246 was replaced with a basic residue, lysine, resulting in a mutant with spectral features identical to P420, the inactive species of P450. But this inactive-species-like mutant showed catalytic activities without the facilitation of any cofactors. By substituting Gly 248 with a histidine, a novel Cys-Fe-His ligation set was obtained in P450cam which represented the very rare case of His ligation in heme-thiolate proteins. In addition to serving as a convenient model for hemoprotein structural studies, the G248H mutant also provided evidence about the nature of the axial ligand in cytochrome P420 and other engineered hemoproteins with thiolate ligations. Furthermore, attempts have been made to replace the proximal ligand in sperm whale myoglobin to construct a heme-thiolate protein model by mimicking the protein environment of cytochrome P450cam and chloroperoxidase.

Development, validation and uncertainty analysis of quantitative structure and activity relationship models for Log P of disinfection by -products

Hydrophobicity as measured by Log P is an important molecular property related to toxicity and carcinogenicity. With increasing public health concerns for the effects of Disinfection By-Products (DBPs), there are considerable benefits in developing Quantitative Structure and Activity Relationship (QSAR) models capable of accurately predicting Log P. In this research, Log P values of 173 DBP compounds in 6 functional classes were used to develop QSAR models, by applying 3 molecular descriptors, namely, Energy of the Lowest Unoccupied Molecular Orbital (ELUMO), Number of Chlorine (NCl) and Number of Carbon (NC) by Multiple Linear Regression (MLR) analysis. The QSAR models developed were validated based on the Organization for Economic Co-operation and Development (OECD) principles. The model Applicability Domain (AD) and mechanistic interpretation were explored. Considering the very complex nature of DBPs, the established QSAR models performed very well with respect to goodness-of-fit, robustness and predictability. The predicted values of Log P of DBPs by the QSAR models were found to be significant with a correlation coefficient R2 from 81% to 98%. The Leverage Approach by Williams Plot was applied to detect and remove outliers, consequently increasing R 2 by approximately 2% to 13% for different DBP classes. The developed QSAR models were statistically validated for their predictive power by the Leave-One-Out (LOO) and Leave-Many-Out (LMO) cross validation methods. Finally, Monte Carlo simulation was used to assess the variations and inherent uncertainties in the QSAR models of Log P and determine the most influential parameters in connection with Log P prediction. The developed QSAR models in this dissertation will have a broad applicability domain because the research data set covered six out of eight common DBP classes, including halogenated alkane, halogenated alkene, halogenated aromatic, halogenated aldehyde, halogenated ketone, and halogenated carboxylic acid, which have been brought to the attention of regulatory agencies in recent years. Furthermore, the QSAR models are suitable to be used for prediction of similar DBP compounds within the same applicability domain. The selection and integration of various methodologies developed in this research may also benefit future research in similar fields.

The relationship between job structure, burnout, and coping methods among public school county bus drivers, bus aides, mechanics, and clerical workers

The purpose of this study was to examine the relationship between the structure of jobs and burnout, and to assess to what extent, if any this relationship was moderated by individual coping methods. This study was supported by the Karasek's (1998) Job Demand-Control-Support theory of work stress as well as Maslach and Leiter's (1993) theory of burnout. Coping was examined as a moderator based on the conceptualization of Lazarus and Folkman (1984). ^ Two overall overarching questions framed this study: (a) what is the relationship between job structure, as operationalized by job title, and burnout across different occupations in support services in a large municipal school district? and (b) To what extent do individual differences in coping methods moderate this relationship? ^ This study was a cross-sectional study of county public school bus drivers, bus aides, mechanics, and clerical workers (N = 253) at three bus depot locations within the same district using validated survey instruments for data collection. Hypotheses were tested using simultaneous regression analyses. ^ Findings indicated that there were statistically significant and relevant relationships among the variables of interest; job demands, job control, burnout, and ways of coping. There was a relationship between job title and physical job demands. There was no evidence to support a relationship between job title and psychological demands. Furthermore, there was a relationship between physical demands, emotional exhaustion and personal accomplishment; key indicators of burnout. ^ Results showed significant correlations between individual ways of coping as a moderator between job structure, operationalized by job title, and individual employee burnout adding empirical evidence to the occupational stress literature. Based on the findings, there are implications for theory, research, and practice. For theory and research, the findings suggest the importance of incorporating transactional models in the study of occupational stress. In the area of practice, the findings highlight the importance of enriching jobs, increasing job control, and providing individual-level training related to stress reduction.^

Solvothermal Synthesis, Structure and Optical Property of Nanosized CoSb3 Skutterudite

Binary skutterudite CoSb3 nanoparticles were synthesized by solvothermal method. The nanostructuring of CoSb3 material was achieved by the inclusion of various kinds of additives. X-ray diffraction examination indicated the formation of the cubic phase of CoSb3. Structural analysis by transmission electron microscopy analysis further confirmed the formation of crystalline CoSb3 nanoparticles with high purity. With the assistance of additives, CoSb3nanoparticles with size as small as 10 nm were obtained. The effect of the nanostructure of CoSb3on the UV–visible absorption and luminescence was studied. The nanosized CoSb3 skutterudite may find application in developing thermoelectric devices with better efficiency. K

The Relationship between Job Structure, Burnout, and Coping Methods among Public School county Bus Drivers, Bus Aides, Mechanics, and Clerical Workers

The purpose of this study was to examine the relationship between the structure of jobs and burnout, and to assess to what extent, if any this relationship was moderated by individual coping methods. This study was supported by the Karasek's (1998) Job Demand-Control-Support theory of work stress as well as Maslach and Leiter's (1993) theory of burnout. Coping was examined as a moderator based on the conceptualization of Lazarus and Folkman (1984). Two overall overarching questions framed this study: (a) what is the relationship between job structure, as operationalized by job title, and burnout across different occupations in support services in a large municipal school district? and (b) To what extent do individual differences in coping methods moderate this relationship? This study was a cross-sectional study of county public school bus drivers, bus aides, mechanics, and clerical workers (N = 253) at three bus depot locations within the same district using validated survey instruments for data collection. Hypotheses were tested using simultaneous regression analyses. Findings indicated that there were statistically significant and relevant relationships among the variables of interest; job demands, job control, burnout, and ways of coping. There was a relationship between job title and physical job demands. There was no evidence to support a relationship between job title and psychological demands. Furthermore, there was a relationship between physical demands, emotional exhaustion and personal accomplishment; key indicators of burnout. Results showed significant correlations between individual ways of coping as a moderator between job structure, operationalized by job title, and individual employee burnout adding empirical evidence to the occupational stress literature. Based on the findings, there are implications for theory, research, and practice. For theory and research, the findings suggest the importance of incorporating transactional models in the study of occupational stress. In the area of practice, the findings highlight the importance of enriching jobs, increasing job control, and providing individual-level training related to stress reduction.

Tobacco use prevention education (TUPE) programs in the state of Florida: Teachers' perceptions of program structure and effectiveness

This study described teacher perceptions of TUPE program effectiveness in Florida in an attempt to improve programs by identifying factors that might influence teacher motivation and performance. Very little work has been done to examine how teachers' perceptions are related to the effectiveness of TUPE programs. A statewide survey provided information about how teachers' perceptions of program effectiveness are affected by variables such as: program structure, barriers, tobacco use norms, and training variables. Data were obtained from a telephone survey conducted in Florida as part of the Tobacco Pilot Project (TPP). The sample included 296 middle school teachers and 282 high school teachers as well as 193 middle school principals and 190 high school principals. Correlational and hierarchical regression analyses identified correlates and predictors of teachers' ratings of effectiveness. Results suggest that use of peer leaders, more frequent evaluations, a higher degree of parent involvement, fewer barriers, greater student interest, and lower tolerance for tobacco use were correlated with higher ratings of program effectiveness. Furthermore, student interest, peer, staff, and community tolerance norms, peer leaders, program evaluation, and parent involvement predicted middle school teachers' perceptions. Parent tolerance, student interest, number of barriers, and more frequent program evaluation predicted high school teachers' perceptions. In addition, middle school teachers who reported a lower number of factors negatively associated with teacher receptivity were more likely to view TUPE programs more favorably than teachers who reported a greater number of these risk factors. This relationship was not as robust among the high school teacher sample. Differences between the middle and high school sample were found in the magnitude and number of significant correlations, the proportion of variance accounted for by predictor variables, and the strength of the relationship between the number of factors negatively associated with teacher receptivity and teachers' perceptions of TUPE effectiveness. These findings highlighted the importance of the timing, program features, and the external environment for enhancing or minimizing teachers' ratings of TUPE program effectiveness. In conclusion, significant increases in TUPE teachers' self-efficacy will occur through the participation of peers, parents, staff, and community leaders in different aspects of TUPE programs. ^

A qualitative study of an interagency relationship: Education interventions for foster children

The Interagency Agreement between the Broward County School System and District 10 Department of Children and Families (DCF) was implemented to improve the organization's relationship and in turn improve education interventions for foster children. The purpose of this study was to examine and describe key decision-makers' perspectives of this interagency relationship after implementing mutual policy. ^ The research questions which drove this study were: (a) from the perspectives of the participants, what was the relationship between the decision-makers of the Department of Children and Families and the Broward County School System, after the implementation of a unification plan that was influenced by the court system? and, (b) how was the relationship between the school system and DCF reflected in the Interagency Agreement? ^ Data were obtained through a case study that included interviews, document analysis and field observations. Participants were key decision-makers in their respective institutional settings and were chosen using criterion sampling. The researcher analyzed and interpreted data from the District 10 DCF commissioned assessment of foster care, the State of Florida Management Plans (education section), the Interagency Agreement, and participant interviews. ^ This study focused on the following five contextual areas regarding the Interagency Agreement: interagency cooperation, interagency coordination, interagency collaboration, traditional organizational linkages, and organizational climate. The results of this study suggest that the organizations' improved relationship improved the educational system for foster children. ^ This researcher recommends that the Interagency Agreement shares the leadership structure with an active parent organization of 15 foster parents who would be divided into three subcommittees. These subcommittees would perform specific tasks such as involving other foster parents, and writing mini proposals to address the social and tutoring needs of foster children. A Wraparound process including community organizations (clubs, businessmen and concerned community groups, Big Brothers/Big Sisters, Boys and Girls Clubs) is also recommended in order to engage foster children in activities to build their social skills, friendships and self-esteem. This researcher also recommends that the Broward County School System consider a role that would provide for the development of curriculum for inservice for teachers. This would empower teachers and allow them to better address the academic and social needs of the foster children. ^

The relationship between alkaloid-based chemical defenses and diet in dendrobatid poison frogs

Chemical defenses are common among organisms and represent some of the most complex adaptations for avoiding predation, yet our understanding of the ecological nature of these systems remains incomplete. Poison frogs are a group of chemically defended organisms that are dependent entirely on diet for chemical defense. In this study, I identified the dietary arthropods responsible for chemical defense in poison frogs, described spatial and temporal patterns in alkaloid composition of poison frogs, and established links between patterns of variation in alkaloid defense and arthropod diet in poison frogs. Identifying dietary sources and studying patterns of variation in alkaloid composition is fundamental to understanding the ecology and evolution of chemical defense in poison frogs. ^ The dendrobatid poison frog Oophaga pumilio shares many alkaloids in common with other poison frogs and is known to vary in alkaloid composition throughout its geographic range. I designed my dissertation to take advantage of these characteristics and use O. pumilio as a model species for the study of chemical defense in poison frogs. Here, I identified siphonotid millipedes as a source for spiropyrrolizidine alkaloids, formicine ants as a source for pumiliotoxin alkaloids, and oribatid mites as dietary sources for the majority of alkaloids found in poison frogs. I found that alkaloid composition varied spatially and temporally, on both small and large scales, within and among populations of O. pumilio. Alkaloid variation between populations was related to geographic distance, and closer populations tended to have alkaloid compositions more similar to each other than to distant populations. ^ The findings of my study suggest that oribatid mites are the most important dietary source of alkaloids in poison frogs. However, overall alkaloid defense in poison frogs is based on a combination of dietary arthropods, including mites, ants, millipedes, and beetles. Variation in chemical defenses of poison frogs is due to (1) spatial and temporal differences in the presence of alkaloids in certain arthropods and (2) differences in the availability of certain alkaloid-containing arthropods, which are likely the result of differences as well as successional changes in forest structure among locations and through time. ^

Social network structure as a critical success condition for open source software project communities

In recent years, a surprising new phenomenon has emerged in which globally-distributed online communities collaborate to create useful and sophisticated computer software. These open source software groups are comprised of generally unaffiliated individuals and organizations who work in a seemingly chaotic fashion and who participate on a voluntary basis without direct financial incentive. ^ The purpose of this research is to investigate the relationship between the social network structure of these intriguing groups and their level of output and activity, where social network structure is defined as (1) closure or connectedness within the group, (2) bridging ties which extend outside of the group, and (3) leader centrality within the group. Based on well-tested theories of social capital and centrality in teams, propositions were formulated which suggest that social network structures associated with successful open source software project communities will exhibit high levels of bridging and moderate levels of closure and leader centrality. ^ The research setting was the SourceForge hosting organization and a study population of 143 project communities was identified. Independent variables included measures of closure and leader centrality defined over conversational ties, along with measures of bridging defined over membership ties. Dependent variables included source code commits and software releases for community output, and software downloads and project site page views for community activity. A cross-sectional study design was used and archival data were extracted and aggregated for the two-year period following the first release of project software. The resulting compiled variables were analyzed using multiple linear and quadratic regressions, controlling for group size and conversational volume. ^ Contrary to theory-based expectations, the surprising results showed that successful project groups exhibited low levels of closure and that the levels of bridging and leader centrality were not important factors of success. These findings suggest that the creation and use of open source software may represent a fundamentally new socio-technical development process which disrupts the team paradigm and which triggers the need for building new theories of collaborative development. These new theories could point towards the broader application of open source methods for the creation of knowledge-based products other than software. ^

Structure of international cooperation in trade, investment and environment

This dissertation analyzes the obstacles against further cooperation in international economic relations. The first essay explains the gradual nature of trade liberalization. I show that existence of asymmetric information between governments provides a sufficient reason for gradualism to exist. Governments prefer starting small to reduce the cost of partner’s betrayal when there is sufficient degree of information asymmetry regarding the partner’s type. Learning about partner’s incentive structure enhances expectations, encouraging governments to increase their current level of cooperation. Specifically, the uninformed government’s subjective belief for the trading partner being good is improved as the partner acts cooperatively. This updated belief, in turn, lowers the subjective probability of future betrayal, enabling further progress in cooperation. The second essay analyzes the relationship between two countries facing two policy dilemmas in an environment with two way goods and capital flows. When issues are independent and countries are symmetric, signing separate agreements for tariffs (Free Trade Agreements-FTA) and for taxes (Tax Treaties-TT) provides the identical level of enforcement as signing a linked agreement. However, linkage can still improve the joint welfare by transferring the slack enforcement power in a case of asymmetric issues or countries. I report non-results in two cases where the policy issues are interconnected due to technological spillover effect of FDI. Moreover, I show that linking the agreements actually reduces enforcement when agreements are linked under a limited punishment rule and policy variables are strategic substitutes. The third essay investigates the welfare/enforcement consequences of linking trade and environmental agreements. In the standard literature, linking the agreements generate non-trivial results only when there is structural relation between the issues. I focus on institutional design of the linkage and show that even if environmental aspects of international trade are negligible linking the agreements might still have some interesting welfare implications under current GATT Rules. Specifically, when traded goods are substitutes in consumption, linking the environmental agreement with trade agreement under the Withdrawal of Equivalent Concession Rule (Article XXVIII) will reduce the enforcement. However, enforcement in environmental issue increases when the same rule is implemented in the absence of linkage.

Proton nuclear magnetic resonance investigation of the native and modified active site structure of heme proteins

Hemoproteins are a very important class of enzymes in nature sharing the essentially same prosthetic group, heme, and are good models for exploring the relationship between protein structure and function. Three important hemoproteins, chloroperoxidase (CPO), horseradish peroxidase (HRP), and cytochrome P450cam (P450cam), have been extensively studied as archetypes for the relationship between structure and function. In this study, a series of 1D and 2D NMR experiments were successfully conducted to contribute to the structural studies of these hemoproteins. ^ During the epoxidation of allylbenzene, CPO is converted to an inactive green species with the prosthetic heme modified by addition of the alkene plus an oxygen atom forming a five-membered chelate ring. Complete assignment of the NMR resonances of the modified porphyrin extracted and demetallated from green CPO unambiguously established the structure of this porphyrin as an NIII-alkylated product. A novel substrate binding motif of CPO was proposed from this concluded regiospecific N-alkylation structure. ^ Soybean peroxidase (SBP) is considered as a more stable, more abundant and less expensive substitute of HRP for industrial applications. A NMR study of SBP using 1D and 2D NOE methods successfully established the active site structure of SBP and consequently fills in the blank of the SBP NMR study. All of the hyperfine shifts of the SBP-CN- complex are unambiguously assigned together with most of the prosthetic heme and all proximal His170 resonances identified. The active site structure of SBP revealed by this NMR study is in complete agreement with the recombinant SBP crystal structure and is highly similar to that of the HRP with minor differences. ^ The NMR study of paramagnetic P450cam had been greatly restricted for a long time. A combination of 2D NMR methods was used in this study for P450cam-CN - complexes with and without camphor bound. The results lead to the first unequivocal assignments of all heme hyperfine-shifted signals, together with certain correlated diamagnetic resonances. The observed alternation of the assigned novel proximal cysteine β-CH2 resonances induced by camphor binding indicated a conformational change near the proximal side.^

Microteaching Lesson Study: Mentor interaction structure and its relation to elementary preservice mathematics teacher knowledge development

This study investigated Microteaching Lesson Study (MLS) and three possible MLS mentor interaction structures during the debriefing sessions in relation to elementary preservice teacher development of knowledge for teaching. One hundred three elementary preservice teachers enrolled in five different sections of a mathematics methods course at a southern urban university were part of the study. This included 72 participants who completed MLS across three different mentor interaction structures as part of their course requirements and 31 elementary preservice teachers who did not complete MLS as part of their methods course and served as a comparison group for a portion of the study. A sequential mixed-methods research design was used to analyze the relationship between MLS mentor interaction structure and growth in preservice teachers' mathematics teacher knowledge. Data sources included pre and post assessments, group developed lesson plans and final reports, a feedback survey with Likert-type and open-ended questions, and transcripts of audio-recorded debriefing sessions. The pre and post assessments were analyzed using Analysis of Variance (ANOVA) and descriptive statistics were used to analyze the Likert-type feedback survey questions. Group MLS lesson plans, final reports, and transcripts of debriefing sessions along with the open-ended questions from the feedback survey were coded in a three-step process as described by Miles and Huberman (1994). In alignment with findings from M. Fernandez (2005, 2010), elementary preservice teachers participating in MLS grew in content knowledge related to MLS topics taught by one another. Results from the analysis of pre and post content knowledge assessments revealed that participants grew in their understanding of the mathematics topics taught during MLS irrespective of their mentor interaction structure and when compared to the participants who did not complete MLS in their methods course. Findings from the analysis of lesson plans for growth in pedagogical content knowledge revealed the most growth in this area occurred for participants assigned to the interaction structure in which the MLS mentor participated in the first two debriefing sessions. Analysis of the transcripts of the discourse during the debriefing sessions and the feedback surveys support the finding that the elementary preservice teachers assigned to the interaction structure in which the MLS mentor participated in the first and second debriefing sessions benefited more from the MLS experience when compared to elementary preservice teachers assigned to the other two interaction structures (MLS mentor participated in only the first debriefing session and MLS mentor participated in only the last debriefing session).