VictorJuiz/thesis huggingface dataset:
Boron tethered intramolecular Diels-Alder cycloadditions and addition of allyl- and crotyltrifluoroborates to carbonyl compounds in biphasic media

This thesis is a summary of research conducted since May 1997 in the laboratories of Professor Robert A. Batey at the University of Toronto. The manuscript is divided into three chapters. Chapter 1 focuses on alkenylboronate tethered intramolecular Diels-Alder reactions. An introduction to the current state of intramolecular Diels-Alder reactions is provided with an emphasis on reactions tethered via a temporary metal/metalloid connection. An efficient new regioselective boron-tethered Diels-Alder reaction using alkenyl boronic esters as the dienophilic component is then described. It was found that the tether length and substitution pattern of the dienyl alcohol had a significant effect on the efficacy and mode of diastereoselectivity of the reaction. Subsequent oxidation of the C-B bond in the cycloadducts, with retention of stereochemistry, lead to the formation of cyclohexenols, which are valuable precursors in natural product synthesis. Conclusive proof of the tethered nature of these cycloadditions was demonstrated by structural characterization of an intermediate boracycle via X-ray crystallography. Overall, the 'E'-alkenyl boronic ester acts as a masked 'E'-enol dienophile. Chapter 2 describes an extension to the above methodology to include dienylboronate tethered Diels-Alder reactions, one of the few methods allowing the use of unactivated dienophiles. The constraining effects of the tether both accelerate the rate of cycloaddition, and control the regio- and stereoselectivity of the reaction. Although the tethered reactions are completely regioselective, they occur with varying diastereoselectivities depending on the substituents present on the dienophile. The development and application of a new class of allyl boron reagents is the subject of Chapter 3. Potassium allyl- and crotyltrifluoroborates were synthesized in good yields and are shown to be air and moisture stable solids that can be stored for extended periods in plastic bottles. These trifluoroborate salts undergo facile addition to aldehydes in a biphasic medium containing a phase transfer catalyst. Potassium allyltrifluoroborate efficiently allylated aliphatic, aromatic, Ã,ß-unsaturated and heterocyclic aldehydes in very high yields and without the necessity of silica gel chromatography. More significantly, crotylations of aldehydes could also be accomplished with excellent diastereoselectivities. Mechanistic studies were also conducted to deduce the mode of reactivity of these reagents.
Drop size dependence of contact angles and line tension

The generalized theory of capillarity identifies line tension as a natural and necessary extension of analysis for the systems with multi-phase boundary curves. Theoretically, finding an estimate for line tension is very complicated. Modeling of molecular interactions almost always requires significant simplifications which would cause considerable uncertainty in the resulting values. Experimentally, line tension is typically small and hence much more difficult to measure than surface tension. A review of the literature shows that there is little consensus among researchers with respect to both sign and magnitude of line tension. Our preferred method to determine line tension for solid-liquid-vapor systems takes advantage of dependence of contact angles on the drop size according to the modified Young equation (Eq. 2.22). Using a sensitive and accurate contact angle and drop size measurement methodology, i.e., Axisymmetric Drop Shape Analysis (ADSA), a large number of contact angle data were produced, i.e., 27, solid-liquid-vapor systems were studied. Potential artifacts that may effect the observed drop size dependence of contact angles including contortions of the three-phase line, solid surface deformation, thin film effect, and heterogeneity of the solid surface, were considered. They all proved insignificant either by the use of models developed to describe and analyze the effect of the particular feature, or by thermodynamic reasoning, or the use of available literature (see section 4.4). It was established that line tension was positive for all of the systems studied. The magnitude of line tension determined ranges from below from 10-7 J/m for systems with low contact angles to 10-4 J/m for the high energy system studied (the range reflects mainly the material properties such as intermolecular forces). Exploratory steps taken to examine line tension behavior near the wetting transition suggested that the line tension decreases as the contact angle decreases and perhaps vanishes at complete wetting. A high energy system, i.e., liquid tin on a silica surface, was also studied. The seemingly large line tension value obtained, i.e., 10-4 J/m, should not be entirely surprising, as it was found that there exists a positive correlation between line tension and solid-liquid interfacial tension.
Mercury-promoted synthesis of substituted 5-aminotetrazoles and studies towards the synthesis of the martinelline alkaloids

This thesis is a summary of research conducted since October 1998 at the University of Toronto in the laboratory of Dr. Robert A. Batey. This manuscript is divided into two chapters. In chapter one, the synthesis of 5-aminotetrazoles ' via' the mercury promoted attack of azide anion on a thiourea is described. The reaction is applicable to mono-, di- and trisubstituted thioureas and represents the first general route to 5-aminotetrazoles of various substitution patterns. Chapter two describes progress towards the synthesis of martinelline, a novel hexahydropyrroloquinoline alkaloid containing three guanidine moieties. Application of the two and three component hetero Diels-Alder methodology is expanded to other dienophiles in attempts to construct the martinelline core 'via' a biomimetic approach. Finally the successful conversion of a tertiary thiourea 4-arylhexahydropyrrolo[3,2-c]quinoline to a guanidine is described for the first time within our labs.
Factors that affect teachers' practices in classrooms with students with disabilities

The purposes of this study were twofold: to test a theoretical framework developed by Stanovich (1994) and Roach (1998) which identifies variables claimed to predict the effectiveness of integration of students with disabilities into classrooms; and to see what can be deduced from changes in teachers' attitudes toward integration of students with disabilities over the 25 year period, 1974 to 1999. A path model of the factors contributing to teachers' practices in integrated classrooms was tested using Lisrel 8.3. The path model was a version of the variables identified in Stanovich's (1994) and Roach's (1998) models, adapted for the current data collection as self-report Likert scales contained in a mailed survey in a large urban school board in Ontario, Canada. Eight hundred and eighty-four elementary teachers of a potential 10,000 responded to the survey. The variables of the model tested to predict the outcome measures of Teachers' Skills and Teachers' Practices were Teachers' Beliefs, Teachers' Attitudes/Placement, Teacher Self Efficacy, and School Norm/Support. The Teachers' Attitudes/Placement measure was weak and was dropped from the final path model solution. The results of the analysis largely confirmed the predicted relationships of the model's components. The path model results indicated that teachers are more likely to use effective teaching practices in an integrated classroom, when they perceive that they have support, have the skills and beliefs to adapt instruction for students with disabilities and consider themselves to be efficacious as teachers. The revised Teachers' Attitudes portion of the present survey replicated a study completed in 1974 (n = 74 teachers) when students with developmental disabilities were first integrated in Ontario (Hambleton & Ziegler, 1974). The Teachers' Attitudes portion was again sent out in 1994 to teachers (n = 140) in large urban school boards in Ontario (Giddens, 1994). Although there have been changes in terminology which affects the interpretation of the findings, a tentative comparison of the three sets of results was made. An analysis of the ranking portion of the survey revealed that teachers are requesting smaller class sizes, supportive administration and that they consider working with parents to be instrumental to their success in integrating students with disabilities.
L'examen d'un processus de changement dans une école élémentaire de langue française du nord de l'Ontario

L'objet de cette étude a été d'examiner un projet d'aménagement linguistique qui s'est réalisé dans un école de langue française dans une ville du Nord de l'Ontario. Ce projet a consisté à mettre en ¶uvre des changements majeurs qui ont eu pour résultat la création d'une école réservée exclusivement linguistique, la directrice a pris ouvertement position en faveur d'un processus sélectif d'admission des élèves. Cet examen s'est fait par le biais de la théorie du changement planifié de Fullan (1991) qui consiste à diviser la processus de changement en examinant trois étapes particulières, soit l'initiation, la mise en ¶uvre et l'institutionnalisation. Certains thèmes-clés ont servi à l'analyse soit la vision commune, la planification flexible, l'initiative et le contrôle, la réaction positive au changement, les ressources pour le personnel et le perfectionnement professional. Le processus de changement planifié a été examiné à partir du point de vue des acteurs sociaux qui ont participé au projet, soit le conseil scolaire, la direction de l'école, le personnel enseignant et les parents. Des entrevues semi-structurées, individuelles et de groupe ont constitué la source principale de données. L'analyse documentaire a également servi á l'analyse présentée. En se basant sur la théorie du changement de Fullan (1991), cette étude examine la raison d'être d'une école homogène dans un milieu où l'assimilation à la culture anglaise majoritaire est une menace constante à la survie de la langue et de la culture françaises. Les résultats ont révélé, selon les personnes interrogées que le processus de changement s'est avéré une réussite. Les élèves du regroupement linguistique ne font plus autant d'erreurs et d'anglicismes dans leur langue parlée et écrite et se disent fiers d'être francophones. La présente étude a permis de mieux saisir les enjeux associés au rôle des écoles de langue française situées en milieu minoritaire, en examinant un type d'école en particulier, celui de l'école homogène exclusivement réservée à une clientèle d'élèves déterminée.
An optical process sensor for steel furnace pollution control and energy efficiency

A near-infrared laser operating in the wavelength region between 1577 and 1582 nm was used to perform 'in-situ' measurements of CO (1577.96 nm), H2O (1577.8 nm and 1578.1 nm) and temperature in the exhaust gas region above a laboratory burner fueled with methane and propane. The applicable range of conditions tested is representative of those found in a commercial electric arc furnace and includes temperatures from 1250-1750 K, CO concentrations from 0 to 10% and H2O concentrations from 3 to 27%. Based on the standard deviation of differences between optical predictions and independently measured values, the minimum accuracy of the technique has been estimated as 36 K for temperature, 0.47% for CO and 3.4% for H2 O. This work represents the first quantitative demonstration that ' in-situ' optical measurement of CO is possible in high temperature combustion off-gases using a standard fiber optic-compatible near-IR TDL. The sensor's ability to non-intrusively measure CO, as well as H2O and temperature in real time will allow for improved process control in industrial combustion applications.
Decolonisation and the narration of international community

The international community is an imagined community, which relies on narratives to construct its identity. Fragments of these narratives can be found in international legal documents such as the Charter of the United Nations. The basis of the international community is not a common identity or a substantive convergence of values but rather a consensus on a common procedure to resolve conflict about values. One of the most persistent narratives of the international community is the assertion that international society is a community of sovereign and co-equal States, which have consented to the international legal order governing their interaction with one another. This narrative was contested during the process of decolonisation. By appealing to the principle of sovereign equality, the newly independent countries revealed how the international community provided rational justification for the suspension of significant international norms--such as sovereign equality--in the treatment of entities deemed to lie beyond the international community.
In the shadow of the economy, judicial decisions on wrongful dismissal in eras of economic uncertainty

The relationship between economy and law is a central issue in sociological theory and research. Yet, few have examined the effects of contemporary economic conditions on legal process. Employment law is one area in which the effects of the economy on legal processes are particularly relevant. With the growth of global economic competition, employers in western nations have actively restructured their operations to reduce employment costs. This transformation in the organization of labour has inundated courts with wrongful dismissal actions. Understanding how courts respond to these actions can provide greater insight into the relationship between law and shifting economic conditions. Three perspectives on the relationship between economy and law guide this dissertation. One perspective suggests that socio-economic context shapes law by influencing the types of cases arriving to court. A second perspective suggests that the combination of socio-economic context and individual characteristics shape legal processes. Finally, neo-institutionalists suggest an endogenous relationship between law and business organizations, with law shaping organizations and organizational interpretations of law in turn shaping law. I examine these perspectives by analyzing judicial decisions on Canadian wrongful dismissal cases. Two sets of wrongful dismissal decisions are collected, coded and analyzed. The first data set is a stratified random sample of reported and unreported wrongful dismissal decisions made in the years between 1970 and 1997. Quantitative analyses show that economic context influences wrongful dismissal judgements by shaping the types of cases arriving to judgement and by interacting with extra-legal factors to produce different case outcomes for different types of plaintiffs. Most importantly, plaintiffs dismissed for economic reasons in the 1990s' recession are treated differently than plaintiffs dismissed for non-economic reasons during the same period and plaintiffs dismissed for economic reasons in other economic periods. Qualitative analyses of judicial decisions on "economic" dismissal provide insight into these findings. The analyses reveal that judges develop particular rationalizations of economic dismissal, which vary according to socio-economic period. In some periods these rationalizations appear to be influenced by business discourses on economic restructuring prevailing in particular economic contexts. I conclude this dissertation by discussing the theoretical, methodological and policy implications of these findings.
Surviving, an exploration of the residual effects of conquering cancer

There has been very little systematic investigation of the long-term effects of the cancer experience. Data produced from the medical mainstream derives from the implicit but pervasive theory that recovery and survival are a function of surgery and/or treatment, and although these advances clearly facilitate healing, this study reveals that recuperation is very much a function of an individual's ability to accept and integrate the many transformations that come with living with cancer. In order to gain further insight into the residual effects of conquering cancer, this thesis explored the needs and concerns of six cancer survivors. A qualitative methodology was selected, and data were gathered via open-ended, in-depth interviews with each participant. The interviews were tape-recorded, transcribed verbatim, and analyzed in order to identify trends regarding survivor's experiences. The research indicated that by continually appraising the meaning of their disease as it related to every aspect of life, the participants in this study experienced varying degrees of Authentic Transformational Integration (ATI). ATI defines a theory that describes a phenomenon which occurred for every research participant enabling him or her to cope more effectively with remission.
The caffeine 8-hydroxylation in humans, a predominantly intestinal phenomenon

The importance of the intestine as a site of drug biotransformation, particularly during drug absorption, is now generally acknowledged. However, development of a method to measure the intestinal drug metabolizing capacity in an individual has been problematic for investigators. A finding of this thesis indicates a possible method to distinguish intestinal drug metabolism from its hepatic counterpart. A traditional pharmacokinetic study of the caffeine 8-hydroxylation to 137U 'in vivo' indicated that this metabolite was formed immediately after caffeine ingestion, prior to the major CYP1A2 mediated N-demethylations. Furthermore, the majority of 137U formation appears to be mediated within the intestine. However, no consistent inhibition of 137U formation by grapefruit juice, an accepted cytochrome P4503A4 inhibitor, was observed. As such, the role of CYP3A4 in 137U formation appears unlikely. Recent evidence of extensive caffeine metabolism by CYP1A1, in combination with documented CYP1A1 presence in the intestine, supports this hypothesis. In conclusion, the relatively earlier formation of 137U as compared to other caffeine metabolites is a novel finding which may be of use in distinguishing between intestinal drug metabolism and its hepatic counterpart.
An analysis of priority setting and resource allocation in Ontario colleges of applied arts and technology

This study examined the decision-making processes for determining priorities and allocating resources in community colleges in Ontario. The study also examined how teaching and learning were considered in relation to resource allocation decision-making. The objectives of this study were accomplished through qualitative analytical methods, using a case study approach of three community colleges in Ontario. This included interviews and a review of college and Ministry of Education and Training documents. The data were collected to cover the period from 1995 to 1999. The following conclusions have been drawn from the study. (1) The decision-making processes for determining priorities and allocating resources used in the three colleges are situational and strongly shaped by the prevailing organizational culture in the individual college. (2) In the colleges where there was more democratic and transparent governance faculty morale and trust were higher. (3) Participation by faculty in resource allocation decision-making in the colleges was varied and incomplete and without power and authority to make a difference in final decisions and implementation. (4) Colleges became more market driven and shifted resources away from teaching and learning into finding alternate sources of funding when public funding declined. (5) Decision-making to allocate resources was more closely linked to politics and to fiscal constraints than to enhancing quality and organizational effectiveness. (6) The findings of this study support the view that the actions of organizations emerge from a combination of the structure of the external environment and the internal behaviour of the organization.
The unique signalling requirements of c-Kit§+ cells stimulated by membrane-bound Steel Factor

Signalling requirements for PI3-kinase and PLC-ã following stimulation of c-Kit+ cells by either soluble Steel Factor or membrane-bound Steel Factor were examined. By studying 32D-KitYF728 and YF719 cells, it was found that PLC-ã activation is required for stimulation by membrane-bound Steel Factor. Stimulation by membrane-bound Steel Factor of 32D cells expressing a wild-type c-Kit receptor was inhibited by neomycin sulfate. Stimulation of bone marrow-derived mast cells by mSLF was inhibited by neomycin sulfate and oleic acid. A study of both antagonists revealed that neither inhibits c-Kit or PLC-ã phosphorylation. PI3-kinase is recruited to the c-Kit receptor following mSLF stimulation of murine bone marrow-derived mast cells. To test the efficacy of the PLC antagonists 'in vivo', the effects of neomycin sulfate and oleic acid were studied in mice. Oleic acid, but not neomycin sulfate, has some potential for reducing overall skin mast cell numbers without visibly affecting surrounding tissue.
Accurate Characterization of Skin Deformations Using Range Data

Generating realistic skin deformations arising from joint movement and muscle contraction is a requirement for producing realistic human character animation. For example, the human arm, hand, or foot change shape in significant ways during motion, ways which are difficult to model accurately with traditional character animation techniques. This thesis suggests a new way to build realistic animated models of the human form. We exploit range image technology to capture the true human form and create parameterized animated surface models based upon this data. The thesis improves in several ways upon the algorithms required to process the range data, as well as presenting a methodology for the required data capture, data integration and surface parameterization. Results are presented for the parameterized flexion of a human arm model.
Development and validation of a model for analyzing the stability of a power wheelchair

Wheelchair stability is a growing concern. Between 25 and 38 percent of serious wheelchair accidents result from forward and backward tips (3, 5, 24). A two dimensional model of a power wheelchair was developed and then validated using a series of static and dynamic tests. Certain wheelchair properties were varied to ensure that the predictions were valid for a wide range of initial conditions. The model was less stable than the actual wheelchair in both static and dynamic scenarios. The model was able to predict static tips within 4.4 degrees and dynamic tips within 3.4 degrees. The model demonstrated that the wheelchair would not tip over upon encountering curbs of up to 7.1 cm high and sudden drops of up to 20.0 cm. The utility of computer modeling as a tool in the design of safer wheelchairs was demonstrated.