Thesis (M.S.)--University of Tennessee Health Science Center, 2009. / Title from title page screen (viewed on October 8, 2009). Research advisor: Edward F. Harris, Ph.D. Document formatted into pages (x1vii, 470 p. : ill.). Vita. Abstract. Includes bibliographical references (p. 151-160).

This thesis comprises three chapters united by a single theme: development of alkali metal cation sensors based on ion complexing macrocycles. In part 1, benzo-18-crown-6 and cryptand 2.2.2B were immobilised on polyacrylic acid backbone through an amide linkage. The benzo-18-crown-6 and 2.2.2B were functionalised using the Friedal-Crafts acylation reaction with ω-amino acids. The spacer between the polymer backbone and the crown ether was varied by using co-amino acids with varying numbers of methylene groups [special characters omitted]. Attempts to use co-amino acids with an intermediate spacer length [special characters omitted] failed due to formation of a cyclic imine. The amino crown ethers were immobilised on a poly(acryloyl chloride). Polymers 2a, 5ad and 6a failed to give self supporting membranes but a polymer blend with PVC/Plasticizer was employed for membrane fabrication. Ion Selective Electrodes (ISEs) and Coated Wire Electrodes (CWEs) were made from polymer blend membranes and their response to alkali metal cations was tested. The ISEs made with mobile carriers were active, while those prepared from immobilised carriers were inactive. The reverse was the case with CWEs. This dichotomy existed in all cases. The selectivity of the ionophores among the alkali metals was unaffected by linkage to the polymer backbone. However, the alkali metal/alkaline earth metal selectivity was enhanced. The effect of plasticizer and hydrophilic additives on electrode response was insignificant. The spacer length had considerable influence: the longer the spacer, the better the electrode response of the CWEs. In part 2, the mass transport of ions across the polymer blend membrane under a temperature gradient was investigated. The immobilised polymers prepared in part 1 were used here to fabricate membranes from polymer blends with NOMEX. In thermodialysis experiments, a low level of ion transport was detected. These preliminary experiments led to a rediscovery of membrane distillation. The scope of this latter process with hydrophobic membranes was explored in detail. Part 3 was devoted to the design and synthesis of water soluble photoionophores. Three series of molecules were synthesised: captands, bis crown ether compounds and phenol derivatives of tartaro crown ether carboxylic adds. Captand molecules were synthesised by a capping reaction of crown ether tetraacid chloride 14 with 1,3-bis(aminomwthyl) benzene, 1,4- bis(aminomethyl) benzene and 2,2’-bis(aminomethyl) biphenyl. Crystals of meta- and para xylene capped molecules were grown and their structures solved to establish the conformation of the molecules. Fluorescence quenching studies of these molecules were done in 0.3% methanol:water (v/v). Quenching due to alkali metal ions was insignificant ( < 20%) while copper and mercury cations quenched the emission significantly ( > 90%). Stern-Volmer analysis showed an upward curvature indicating association between the ligand and the cations [special characters omitted] cations, but dynamic and static components of the quenching could not be separated. Potentiometric titration with a potassium selective electrodes was carried out to obtain the stability constants for these ligands with potassium ion. The bis crown ethers 28 and 29, designed to increase water solubility, were prepared by the reaction of anhydride 27 with 9,10-bis(ammomethyl) anthracene and 1,2-bis(aminomethyl) benzene. The pKa values of the ligands and their stability constants with alkali and alkaline earth metal ions were determined by potentiometric titration. Fluorescence quenching studies were done in aqueous buffer at pH 10. These compounds also failed to give an emission quenching in the presence of alkali or alkaline earth metal cations, but both copper and mercury cations showed a significant amount of quenching. Stability constants were derived from emission quenching studies for [special characters omitted]. Chromoionophores, phenol derivatives of tartaro crown ethers, were synthesised from the reaction of crown ether anhydrides and 2-aminophenol. The structure of the compound 31 was assigned as the syn isomer based on nmr data in comparison to literature reports. Absorption studies were carried out in water. The absorption spectra of compound 30 were perturbed by alkali metal as well as alkaline earth metal ions, while the absorption spectrum of compound 31 showed no response to varying cation concentration. The lack of response from compound 31 was attributed to the competitive binding of cations among syn carboxylic groups away from the syn phenolic groups. / Graduate

This work is an interdisciplinary exploration of negotiations between the nations that make up Canada. It explores the disparity that remains between Aboriginals and non Aboriginals in Canadian North America at a systemic level. It will show that the postcolonial era is rampant with colonial doctrine and that these principles and policies maintain a dogmatic system that can not allow for the continued existence of Aboriginals as separate and distinct peoples. I will show my understanding and interpretation of an old Indigenous system and suggest ways in which aspects of this ancient system may be valuable in creating a coordination of world views that can allow for both factions to exist and prosper. I will specifically address how the differing world views that exist between Aboriginal and non-Aboriginal Canadians—and the inequality between these two groups of peoples—has been and remains infused in the negotiation process that these governments attempt to complete. The final aspect of this work will be a theatrical production piece that allows (in some small way) the traditional Indigenous approach to ‘law’ to be given equal weight as the Supreme Court in Delgamuukw suggests. / Law, Faculty of / Graduate

The history of the disposal of Crown lands in British Columbia is in reality the history of the economic development of the province. It covers the progress of British Columbia from its days as a hunting and trading preserve of the Hudson's Bay Company through its brief colonial period and formative years as a province down to its years of rapid settlement and development in the decade before 1913. Once the colonial period had passed, the attack upon the natural resources began in earnest. So rich and abundant did those resources of land, mine, forest, and water prove that British Columbia found itself launched into an industrial era almost before adequate legislation had been framed to deal with its land and resources. Legislation was necessary to guide the economic progress of the province and to establish regulations governing the disposal of Crown land and its appurtenant resources of mineral, timber, and water. The laws were framed always with a view to accomplishing three things - encouraging settlement, forestalling speculation, and securing revenue. Since in every case the basis of provincial legislation was to be found in the proclamations and ordinances framed from 1858 to 1864 by Governor Douglas, a survey of colonial regulations is needed to clarify subsequent policy. To assist him in framing proclamations for guiding the progress of the two colonies, Douglas looked to the Colonial Office, the terms under which the Hudson’s Bay Company had held Vancouver Island, and his own judgment. The first regulations adhered closely to principles laid down by the Colonial Office. Douglas was carefully instructed to ward off speculation in public lands by making beneficial use of the criterion of alienation. No agricultural land was to be pre-empted other than by bona fide settlers. Land was not to be sold without some guarantee that it would be improved. Timber leases were to be granted only to the operators of saw Mills. Miners could not divert water from streams unless it was needed at once. By 1871 the principle of beneficial use had been so thoroughly established in law that it was never thereafter abandoned. Practice, however, was at variance with principle and until the McBride ministry had devised adequate administrative machinery after 1909 little could be done to enforce regulations. Secondly, Douglas was instructed to reserve certain rights to the Crown. Gold, wherever found, was so reserved; by 1913, silver, coal, natural gas, and oil had been added. Land for government purposes was similarly reserved to the Crown. As for other principles, Douglas found he could not enforce them in the face of existing conditions. Sale of land by auction did not work, nor did insistence upon immediate payment. Neither principle could prevail for long. To secure money, Douglas soon discovered he must dispose of lands on easy terms. Had the Colonial Office seen fit to heed Douglas's plea to lend credit to the new Pacific colonies to relieve them of the pressing need for money, the subsequent wholesale alienation of large tracts of the best land at very low prices would have been unnecessary. Beneficial use, sale only by auction, cash sales, and survey prior to alienation could all have been firmly established and carefully supervised. As it was, British Columbia did none of these things and indeed, became the only province in Canada where land could be alienated prior to survey. Prom 1871 to 1913 British Columbia followed the pattern set in colonial days. The only reason the province retained ninety per cent of the timber stands was that, before legal safeguards were enacted, timber was regarded more as a nuisance than as an asset. But the necessity for securing revenue by selling or otherwise disposing of Crown lands on as easy terms as possible established a pattern of thinking that was to see the reckless alienation of millions of acres of land to railway promoters between 1883 and 1900. Much of the land was later repurchased. And because of the difficulties which arose between the Dominion and the province over jurisdictional conflicts stemming from the presence of a forty-mile strip of land through the heart of the province granted in exchange for rail connections with eastern Canada, enough ill-feeling was engendered to make the allotting of Indian reserve lands one of the most vexed problems In provincial history. Crown lands in unlimited quantity were disposed of to land and timber speculators and railway promoters from 1871 to 1900. Not until 1900 did provincial governments begin to question the wisdom of such wholesale alienation. Land was so eagerly sought from 1905 to 1913 that effective machinery was finally devised to regulate its disposal on terms most favourable to the province. Pre-emptions were inspected, water rights were clarified, timber lands were placed under reserve for sale of the timber by auction only, extensive surveys of agricultural lands were made, and settlement was at last directed to areas served by communication facilities. By 1913 Crown lands and their natural resources were recognized for what they were - priceless expendable assets and the people’s heritage - no longer to be disposed of heedlessly but rather to be conserved for posterity. / Arts, Faculty of / History, Department of / Graduate

The marginal fringe region of Canada is an agricultural area which is near the environmental and economic limits for commercial agricultural production. Combinations of physical factors and social and economic influences result in an area that experiences dramatic shifts in land use and agricultural development. Government policy is, however, a potentially significant controlling and stabilizing factor in the region's development. It is therefore fundamentally important that government plan its diverse functions and responsibilities in the marginal fringe to ensure an effective, equitable and efficient allocation of society's scarce resources. This thesis analyses existing planning programs for the development of agriculture on Crown land in Canada's marginal fringe region. It seeks to determine whether these programs have the potential to ensure the efficient and equitable development of agricultural land. This thesis also addresses the problem of how we should effectively develop our shrinking supply of undeveloped arable land and whether existing planning programs adequately address the major issues in the development process. The methods of investigation include a series of three case studies: St. John's, Newfoundland; Fort Nelson, British Columbia and; Fort Vermilion, Alberta. The case studies are analysed using a framework based on an idealized planning process developed in-the first chapter. This framework is applied to representative planning exercises in each case in order to illustrate the overall planning program's strengths and weaknesses. Based on this broad analysis, I present, in conclusion, the most crucial questions for developing effective planning programs in the marginal fringe and apply these questions to the cases studied. Official reports and surveys, detailed correspondence, personal and telephone interviews, and first-hand experience form the basis for analysis in the case studies. A literature review is the basis for the contextual elements developed in Part I of this thesis. The results of this study raise a number of concerns about existing planning programs for the agricultural development of Crown land in the marginal fringe, particularly in British Columbia and Newfoundland. The crucial issues for developing effective planning programs in the marginal fringe include the need for a clearly articulated, stable yet flexible, program focussing on the marginal fringe region. The agricultural lead agency's involvement is crucial for these programs. Further questions consider how well environmental factors are inventoried, evaluated and communicated to decision-makers; whether adequate socio-economic assessments are permitted; if alternative resource development options to agriculture are considered; whether government programs related to agricultural development are effective or whether they are inconsistent with planning program objectives, and whether the public understand and support the planning program. Planning the agricultural development of Crown land in the marginal fringe is in its infancy. Sudden changes to programs, as in British Columbia, and funding deadlines, as in Newfoundland, are harmful to the efficient and effective development of frontier resources and they erode government credibility. Some jurisdictions, such as Alberta, are making rapid strides in applying many of the traditional planning techniques, although social and economic assessment is very weak or absent altogether in each of the programs studied. Usually, decisions are based on a narrow assessment of environmental factors and there are often significant gaps in essential data, especially climate. Alternative resource development options to agriculture are seriously considered only in British Columbia. Only in Alberta has the vital element of public support begun to be appreciated. Elsewhere, public involvement is, more or less, neglected or mishandled. In conclusion, this thesis raises a number of issues requiring future research, related mainly to socio-economic assessment and planning program development. Also a series-of more detailed normative principles are offered for the improvement of planning programs for the agricultural development of Crown land in the marginal fringe. / Applied Science, Faculty of / Community and Regional Planning (SCARP), School of / Graduate

Magister Scientiae Dentium - MSc(Dent) / Provisional crown and fixed partial denture (bridge) materials are often referred to as "temporary" materials. The Oxford Dictionary defines temporary as "lasting, or meant to last only for a time; not permanent". Yet for crown and fixed partial denture restorations a provisional restoration is crucial to the final restoration. It is, or should be, a preview of the final prosthesis.

Recent outbreaks of mountain pine beetle (Dendroctonus ponderosae Hopkins) in lodgepole pine (Pinus contorta Dougl. ex Loud. var. latifolia Engelm.) forests and spruce beetle (Dendroctonus rufipennis Kirby) in Engelmann spruce (Picea engelmannii Parry ex Engelm.) forests have affected vast areas across western North America. The highlevels of tree mortality associated with these outbreaks have raised concerns amongst fire managers and wildland firefighters about the effects of the tree mortality on fire behavior, particularly crown fire behavior, as crown fires hinder the ability of firefighters to conduct safe and effective fire suppression operations. Current information regarding crown fire dynamics in recently attacked forests is limited to results obtained from simulations employing either inappropriate and/or unvalidated fire behavior models based on inadequate descriptions of crown fuel flammability. The purpose of this research was to measure and characterize the changes in crown fuel flammability caused y recent bark beetle attack and to describe the implications of these changes on crown fire potential in affected forests. Results indicated that bark beetle attack causes a significant decline in moisture content and change in chemical composition in lodgepole pine and Engelmann spruce tree foliage, which substantially increases foliage flammability. Additionally, it was found that conventional models used to predict the moisture content of fine, dead surface fuels were inappropriate for predicting the moisture content of foliage on mountain pine beetle-attacked lodgepole pine trees during the red stage. Therefore, calibrated operational models and models based on diffusion theory were developed and evaluated that could accurately predict hourly fluctuations in moisture content. The implications of these changes on crown fire potential are dependent upon a host of site specific factors including outbreak duration, severity, and the specific stand characteristics. Based on our results, we believe that current fire behavior models, including popular semi-empirical and physics-based models, are currently inadequate for accurately predicting crown fire potential in forests recently attacked by bark beetles. In order to make significant progress in our understanding of crown fire potential in recently attacked forests, a substantial effort to document wildfire behavior in the field and/or to conduct experimental fires is needed.

Abstract Introduction: Patients with numerous crowns and bridges are at risk of developing secondary caries on cervical margins of the crowns. This recurrent decay accounts for 60% of the reasons for the replacement of restorations. Detection and treatment of subclinical lesions is important to prevent cavitation. An alginate impression material has been used to locate cariogenic bacteria in established carious lesions. Aims: An alginate impression technique was used to assess the level of Streptococcus mutans and Lactobacilli on the crown margins of the teeth of the restored group and control subjects. Conventional caries activity tests were also used to compare these two groups. Methods: Twenty control group subjects with no crowns and a mean DMFS of 16 and 20 the restored group patients with at least 10 crowns and a mean DMFS of 129 were included in the study. Impressions were taken with a hydrocolloid material mixed with culture broth, incubated and examined for the presence of S. mutans and Lactobacilli on the cervical margins. The results were compared using the two-sample t-test, chi-squared test and a generalized logistic regression analysis. Results: More S. mutans and Lactobacilli were cultured on impressions of the restored group than the control patients (p=0.01 and 0.002). A higher proportion of patients in the restored group had high concentrations of S. mutans and Lactobacilli on their teeth than subjects in the control group (p < 0.001). In the restored group, sixty six per cent of teeth in the posterior and 48% in the anterior segment were crowns. S. mutans and Lactobacilli were found in higher concentrations on the posterior than the anterior teeth of the restored group patients than the control patients (p = 0.016 and 0.047). Furthermore, more Lactobacilli were cultured from the saliva of the restored group than control subjects while the buffering capacity of plaque and the ability of saliva to neutralize acids were lower in the restored group than control group subjects. Conclusion: The impression technique showed that S. mutans and Lactobacilli accumulated in the posterior of the mouth and were associated with crowns indicating these particular sites are at risk.

In the absence of canopy-opening disturbances, upland oak forests in the eastern United States are shifting to shade-tolerant, fire-sensitive tree species (i.e. mesophytes) via a hypothesized positive feedback loop of less flammable, self-promoting conditions, termed mesophication. To evaluate species-specific impacts on mesophication, I quantified canopy, bark, and leaf litter traits of five hypothesized mesophytes [red maple (Acer rubrum), sugar maple (A. saccharum), American beech (Fagus grandifolia), hickory (Carya spp.), and tulip poplar (Liriodendron tulipifera)] and four upland oaks [black oak (Quercus velutina), chestnut oak (Q. montana), scarlet oak (Q. coccinea), and white oak (Q. alba)] in central Kentucky. Red maple, sugar maple, and American beech had increased canopy depth with stem size, smoother bark, and small, thin leaves when compared to oaks. My findings suggest that some mesophytes, such as red maple, sugar maple, and American beech, may decrease future forest flammability by reducing understory light and increasing fuel moisture.

The purpose of this research is to explore through a critical lens the ways in which independence planning for crown wards is reflected in recording documents and the extent to which such documentation suggests the nature of continued involvement with the youth in such planning processes. Data were gathered by examining planning documents used by Child Welfare agencies in Ontario for crown wards. To accommodate the evolving emergence of themes and conceptual patterns revealed in the data, a grounded theory approach and constant comparative method was used as detailed by Charmaz (2006). Independence planning involved crown wards in developing visitation plans with members of the family of origin, and included goal setting pertaining to the development of social skills and acquisition of educational qualifications and instrumental skills. The planning documents lacked specific behavioural examples, contextual understanding, specific examples of the efforts undertaken by CAS workers and caregivers to support goals, and examples of discussions between workers and crown wards. Planning documents generally reflected little involvement of the crown ward. Planning and OnLAC documents require modification so as to allow for and encourage qualitative information and greater input from the crown ward. Such modifications ought to be understood by Child Welfare management in terms of making planning processes more useful and beneficial to crown wards and CAS workers. / Thesis / Master of Social Work (MSW)