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.^

Secondary school inclusion rates: The relationship between the training and beliefs of school site principals and the implementation of inclusion

Programs require strong support and guidance from those in leadership positions to ensure proper implementation (Fullen, 2001). Consequently, school site principals must rely on the training they have received to support them in making appropriate decisions. It is the school site principal’s leadership that is pivotal in the success of students with disabilities (DiPaola & Walther-Thomas, 2003; Monteith, 2000). In fact, the principal has a moral obligation to provide an environment that supports social justice in schools (Grogan & Andrews, 2002). The inclusion of students with disabilities does just that—it ensures that these students are not segregated to a “separate but equal” education. This study utilized a participant survey to collect data on principals’ beliefs and training in special education. This information was compared to the percentage of time students with disabilities spent with their non-disabled peers in the principals’ respective schools. An analysis was conducted to identify if a linear relationship exists between the selected variables and the inclusion percentages. Open-ended questions were included in the original survey which allowed for a thematic analysis of the responses. These responses were utilized to allow participants to further express their thoughts on the identified variables. Results indicated that there were no statistically significant relationships identified between the beliefs and training of secondary school site principals and the percentage of time that their students in special education spend with their non-disabled peers. Although the original research questions were not supported, further post hoc analysis indicated that the results obtained did support that the principals believed inclusion had a social benefit to students. Additional investigation into the academic benefits of inclusion is still needed. In addition, principals who indicated that they had some type of training in special education indicated a higher percentage that the individual student should be the focal point when making placement decisions. These results support the need for further research in the area of principal preparation programs and their relationships to the daily practice of school site principals.

An analytical investigation into shear wall and slab interconnections between reinforced concrete modules for high -rise buildings utilising modular construction under extreme seismic and wind loading

This research investigates a new structural system utilising modular construction. Five-sided boxes are cast on-site and stacked together to form a building. An analytical model was created of a typical building in each of two different analysis programs utilising the finite element method (Robot Millennium and ETABS). The pros and cons of both Robot Millennium and ETABS are listed at several key stages in the development of an analytical model utilising this structural system. Robot Millennium was initially utilised but created an analytical model too large to be successfully run. The computation requirements were too large for conventional computers. Therefore Robot Millennium was abandoned in favour of ETABS, whose more simplistic algorithms and assumptions permitted running this large computation model. Tips are provided as well as pitfalls signalled throughout the process of modelling such complex buildings of this type. ^ The building under high seismic loading required a new horizontal shear mechanism. This dissertation has proposed to create a secondary floor that ties to the modular box through the use of gunwales, and roughened surfaces with epoxy coatings. In addition, vertical connections necessitated a new type of shear wall. These shear walls consisted of waffled external walls tied through both reinforcement and a secondary concrete pour. ^ This structural system has generated a new building which was found to be very rigid compared to a conventional structure. The proposed modular building exhibited a period of 1.27 seconds, which is about one-fifth of a conventional building. The maximum lateral drift occurs under seismic loading with a magnitude of 6.14 inches which is one-quarter of a conventional building's drift. The deflected shape and pattern of the interstorey drifts are consistent with those of a coupled shear wall building. In conclusion, the computer analysis indicate that this new structure exceeds current code requirements for both hurricane winds and high seismic loads, and concomitantly provides a shortened construction time with reduced funding. ^