Measurement of forces between and within bilayers of neutral phospholipids

Phospholipids in water form lamellar phases made up of alternating layers of water and bimolecular lipid leaflets. Three complementary methods, osmotic, mechanical, and vapour pressures, were used to measure the work of removing water from lamellar phases composed of frozen dipalmitoylphosphatidylcholine ( DPPC ), melted DPPC, egg phosphatidylethanolamine or equimolar mixtures of DPPC and cholesterol ( DPPC/CHOL ), Concurrently the structural changes that resulted from this water removal were measured using X-ray diffraction. The work was divided into that which forces the bilayers together ( F ) and that which compresses the molecules together within the bilayers ( F )# A large repulsive force exists between bilayers composed of each of the lipids studied and this force increases exponentially as bilayer separation is decreased. F is affected by the nature of the head groups, conformation of the acyl chains and heterogeneity of these chains. In general all of the melted phosphatidylcholines ( melted DPPC, egg lecithin and DPPC/CHOL ) have large equilibrium separations in excess water resulting from large repulsive hydration forces between these bilayers. By comparison, egg PE has an increased attractive force, and frozen DPPC has a decreased hydration force; each results in smaller separations in water for these two lipids. The chemical potentials of the water between the bilayers for all these lipids lie on a continuum, indicating that interbilayer water cannot be characterized by two discrete states, usually referred to as "bound" or "non**bound". For all lipids studied a maximum of 25 % of the total work done on the system goes into deforming the bilayers. The method used here viii to separate repulsion from deformation, developed for us by v. A. Parsegian, provides a unique method for the measurement of lateral pressure of a bilayer and its modulus of deformability ( Y ). Lateral pressure is affected by the nature of the head group, conformation and heterogeneity of the acyl chains. For small changes in molecular surface area ( A ) near equilibrium, both melted and frozen DPPC have similar values for the deformability modulus. Thus in this regime it requires about the same force to change the angle of tilt of frozen chains as it does to compress the fluid bilayer. The introduction of cholesterol into bilayers of DPPC reduces dramatically the lateral pressure of the bilayers over a large range of molecular surface areas ( A ). The variation in the magnitude of bilayer repulsion with different phospholipids provides a basis for the mechanism of lipid segregation in mixed lipid systems and suggests that interacting heterogeneous membranes may influence or modulate the composition of the opposing membrane. The measurements of deformabilities of bilayers provides a direct comparison of them with the properties of monolayers.

The effect of a weighted-vest strength and balance training program on obstructed walking in postmenopausal women

SUMMARY Background: Age related declines in lower extremity strength have been associated with impaired mobility and changes in gait patterns, which increase the likelihood of falls. Since community dwelling adults encounter a wide range of locomotor challenges including uneven and obstmcted walking surfaces, we examined the effect of a strength 11 and balance exercise program on obstructed walking in postmenopausal women. Objectives: This study examined the effect of a weighted-vest strength and balance exercise program on adaptations of the stance leg during obstacle walking in postmenopausal women. Methods: Eighteen women aged 44-62 years who had not engaged in regular resistance training for the past year were recruited from the St. Catharines community to participate in this study. Eleven women volunteered for an aerobic (walking), strength, and balance training program 3 times per week for 12 weeks while 7 women volunteered as controls. Measurements included: force platform dynamic balance measure of the center of pressure (COP) and ground reaction forces (GRFs) in the stance leg while going over obstacles of different heights (0,5, 10,25 and 30 cm); and isokinetic strength measures of knee and ankle extension and flexion. Results: Of the 18 women, who began the trial, 16 completed it. The EX group showed a significant increase of 40% in ankle plantar flexion strength (P < 0.05). However, no improvements in measures of COP or GRFs were observed for either group. Failure to detect any changes in measures of dynamic balance may be due to small sample size. Conclusions: Postmenopausal women experience significant improvements in ankle strength with 12 weeks of a weighted-vest balance and strength training program, however, these changes do not seem to be associated with any improvement in measures of dynamic balance.

An inquiry into the barriers to participation within the fitness industry for people living with mobility challenges

This qualitative study was designed to inquire about the barriers to participation within the fitness industry for people living with mobility challenges. i\n examination of the insights, stolies~ and experiences with barriers through interviews gi ven by 4 people living with mobility challenges (PMC) formed the core of the research. An analysis of the interviews from the 4 PMC informants was performed at t\\/O levels. First, a content analysis served to identify general and specific categories related to barrier issues within various fitness environments. Secondly, in-depth thematic analyses of the entries related to the insights and stories from the 4 informants which emerged from the content analysis of the data gave rise to fi ve thematic statements. From the thematic statements a fitness industry awareness protocol was created in the fonn of a statement response questionnaire. The protocol, which was given to 4 fitness assessors/trainers, \vas used to provide a snapshot of the fitness industry's readiness to work vvith disability. Throughout the process, the four PNIC informants formed a collaborati vely involved group of coresearchers, adding their voices to the narrative of the fitness-barrier experience. The result of the study suggests that barriers to participation within the fitness industry for PMC exist in various forms and levels of severity. The results also suggest that the fitness industry needs to better prepare their people and environment for working with people with physical disabilities, such as PMC, and provide a more open and positi ve environment for participation. Within the context of any fitness-related environment, recognizing that barriers to participation do exist, and acknowledging and accepting people with disabilities for who they are as indi viduals, will serve to develop a relationship where fitness practitioners and people with disabilities can work towards creating an inviting, inclusive, accessible, and barrier-free fitness environment for all.

Calculation of nondifferential properties for atomic ground states /

A new method for sampling the exact (within the nodal error) ground state distribution and nondiflPerential properties of multielectron systems is developed and applied to firstrow atoms. Calculated properties are the distribution moments and the electronic density at the nucleus (the 6 operator). For this purpose, new simple trial functions are developed and optimized. First, using Hydrogen as a test case, we demonstrate the accuracy of our algorithm and its sensitivity to error in the trial function. Applications to first row atoms are then described. We obtain results which are more satisfactory than the ones obtained previously using Monte Carlo methods, despite the relative crudeness of our trial functions. Also, a comparison is made with results of highly accurate post-Hartree Fock calculations, thereby illuminating the nodal error in our estimates. Taking into account the CPU time spent, our results, particularly for the 8 operator, have a relatively large variance. Several ways of improving the eflSciency together with some extensions of the algorithm are suggested.

From the ground up : understanding how teachers and administrators make sense of tension

Strategies designed to improve educational systems have created tensions in school personnel as they struggle to respond to competing demands of ongoing change within their daily realities. The purpose of this case study was to investigate how teachers and administrators in one elementary school made sense ofthese tensions and to explore the factors that constrained or shaped their responses. A constructive interpretative case study using a grounded theory approach was used. Qualitative data were collected through document analysis, semi-structured interviews, and participant observation. In-depth information about teachers' and administrators' experiences and a contextual understanding oftension was generated from inductive analysis of the data. The study found that tension was a phenomenon situated in the context in which it arose. A contextual understanding of tension revealed the interactions between the institutional, personal, and emotional domains that continually shaped individual and group behavioural responses. This contextual understanding of tension provided the means to reinterpret resistance to change. It also helped to show how teachers and administrators reconstructed identities and made sense in context.. Of particular note was the crucial nature of the conditions under which teachers and adlninistrators shaped meaning and understood change. This study sheds light on the contextual intricacies of tension that may help leaders with the complex design and implementation of educational change..

The application of the structural correlation method to determine the reaction coordinate for a putative ring closure reaction

The cr ystal structure of the compound 2-benzoylethylidene-3-(2,4- dibromophenyl)-2,3-dihydro-5-phenyl-l,3,4-thiadiazole* C23H16Br2NZOS (BRMEO) has been determined by using three dimensiona l x-ray diffraction data. The crys tal form is monoclinic, space group P21/c, a = 17.492(4), o -.t' 0 R 0 b =: 16.979(1), c = 14.962(1) A, "X. =o= 90 ',= 106.46(1) , z = 8, graphite-monochromatized Mo~ rad iation, Jl= 0.710J3~, D = 1.62g/cc and o D = 1.65g/cc. The data were col lected on ~ Nonius CAD-4 c diffractometer. The following atoms were made anisotropic: Br, S, N, 0, C7, and C14-C16 for each i ndependent molecu le ; the rest were left isotropic. For 3112 independent refl ec tions with F > 6G\F), R == 0.057. The compound has two independent molecules within the asymmetric unit. Two different conformers were observed which pack well together. /l The S---O interaction distances of 2.493(6) and 2 . 478(7) A were observed for molecules A and B respectively. These values are consistent with earlier findings for 2-benzoylmethylene-3-(2,4-dibromophenyl)- ~~ 2,3-dihydro-5-phenyl-l,3,4-thiadiazole C22H14Br2N20S (BRPHO) and 2-benzoylpropylidene-3-(2,4-dibromophenyl)-2,3-dihydroiii ,'r 5-phenyl-l,3,4-thiadiazole C24H18Br2N20S (BRPETO ) where S---O distances are l ess than the van der Waals (3.251\) but greater than those expected for () a single bond (1.50A). From the results and the literature it appears obvious that the energy/reaction coordinate pathway has a minimum between the end structures (the mono- and bicyclic compounds). * See reference (21) for nomenclature.

Modifications to the Suzuki reaction and mechanistic insights on the NBS mediated cleavage of benzylidene acetals /

One of the most challenging tasks for a synthetic organic chemist today, is the development of chemo, regio, and stereoselective methodologies toward the total synthesis of macromolecules. r . The objective of my thesis was to develop methodologies towards this end. The first part of my project was to develop highly functionalized chirons from D-glucose, a cheap, chiral starting material, to be utilized in this capacity. The second part of the project dealt with modifying the carbon-carbon bond forming Suzuki reaction, which is utilized quite often as a means of combining molecular sub units in total synthesis applications. As previously stated the first area of the project was to develop high value chirons from D-glucose, but the mechanism of their formation was also investigated. The free radical initiated oxidative fragmentation of benzylidene acetals was investigated through the use of several test-case substrates in order to unravel the possible mechanistic pathways. This was performed by reacting the different acetals with N-bromosuccinimide and benzoyl peroxide in chlorobenzene at 70^C in all cases. Of the three mechanistic pathways discussed in the literature, it was determined, from the various reaction products obtained, that the fragmentation of the initial benzylic radical does not occur spontaneously but rather, oxidation proceeds to give the benzyl bromide, which then fragments via a polar pathway. It was also discovered that the regioselectivity of the fragmentation step could be altered through incorporation of an allylic system into the benzylidene acetal. This allows for the acquisition of a new set of densely functionalized. chiral, valuable synthetic intermediates in only a few steps and in high yields from a-Dglucose. The second part of the project was the utilization of the phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) as an efficient reusable medium for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts of water and toluene using potassium phosphate and 1% Pd2(dba)3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and afforded complete conversion within 1 hour at 50 ^C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70 ^C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system in which the top hexane phase contained the biaryl products, the palladium catalyst remained fully dissolved in the central THPC layer, while the inorganic salts were extracted into the lower aqueous phase. The catalyst was then recycled by removing the top and bottom layers and adding the reagents to the ionic liquid which was heated again at 50 ^C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences.

The journey towards comprehensive school health within an aboriginal community

The purpose of this research is to describe the journey towards Comprehensive School Health at two Aboriginal elementary schools. An advocate and a healthy schools committee were identified at both schools and were responsible for developing initiatives to create a healthy school community. A case study was used to gather an in-depth understanding of Comprehensive School Health for the two schools involved. As a researcher, I functioned within the role of a participantobserver, as I was actively involved in the programs and initiatives completed in both schools. The research process included: the pilot study, ethics clearance and distribution of letters of invitation and consent forms. Data collection included 16 semi-structured, guided interviews with principals, teachers, and stupents. Participant observations included sites of the gymnasium, classroom, playgrounds, school environments, bulletin boards as well as artifact analysis of decuments such as school newsletters, physical education schedules and school handbooks. The interviews were transcribed and coded using an inductive approach which involves finding patterns, themes and categories from the data (patton, 2002). Research questions guided the findings as physical activity, physical education, nutrition and transportation were discussed. Themes developed t~rough coding were teacherstudent interactions, cultural traditions, time constraints and professional development and were discussed using a Comprehensive School Health framework.

Postcolonial entanglements of Power, Race, Class and Privilege in Child and Youth Care Work Within a Brazilian Favela

This research assesses the various aspects of Child and Youth Care (CYC) work and how relationships between child or youth and care provider are limited and constricted within greater political, social and historical contexts. Specifically, this research takes place internationally in Rio de Janeiro, Brazil within a favela (slum) and unveils the entangled and complex relationship that I, not only as an ethnographer, but also as a CYC worker had with the many young people that I encountered. It will address a variety of theories that demonstrate the potentials of reproducing oppressive relationships, and argue that it is imperative for CYC workers to critically reflect on the greater contexts in which their work is situated in order to gain forces with those young people whom they are attempting to serve.

DFT Studies of the Organocatalytic Aldol Reaction and a Frustrated Lewis Pair

The computational study, and in particular the density functional theory (DFT) study of the organocatalytic α-chlorination-aldol reaction and the chiral backbone Frustrated Lewis Pair (FLP) system served as a valuable tool for experimental purposes. This thesis describes methods to consider different transition states of the proline- catalyzed α-chlorination aldol reaction to determine the reasonable transition state in the reaction between the enamine and α-chloro aldehydes. Moreover, the novel intramolecular Frustrated Lewis pair based on a chiral backbone for the asymmetric hydrogenation of imines and enamines was designed and the ability of hydrogen splitting by this new FLP system was examined by computational modeling and calculating the hydrogen activation energy barrier.