Introduction: Oxidative stress is a disruption in the balance of free radicals and antioxidants. Cancer patients have very high levels of oxidative stress due to radiation and chemotherapy. This imbalance from the oxidative stress can stimulate cancerous growth, as well abnormal cellular growth. Oxidative stress is due, in part, to lipid per-oxidation from cancer treatments, generating electrophilic aldehydes that attack abnormal, as well as healthy cells. A way to combat the amount of oxidative stress to protect healthy cells is to increase antioxidant defenses through the diet. Antioxidants are chemicals that help stop free radical formation and prevent cell damage. Traditional high antioxidant foods include fruits, vegetables, low saturated- fats, and high fiber foods. During cancer treatments the patient generally has a decreased sense of appetite, as nausea and emesis are common side effects. A “treat” food, like a Reese’s peanut butter cup might be able to stimulate a cancer patient’s appetite, and thus meeting some of their much-needed dietary nutrients. By transforming this popular dessert treat into something that could aid with oxidative stress may be beneficial to this population. The objective of this study was to create an appetizing and nutritionally functional Reese’s peanut butter cup alternative with enhanced antioxidants. Methods: A common Reese’s cup recipe was taken and adapted for more nutrient rich ingredients. The milk chocolate of the original control recipe for Reese's cup was substituted in the variant dessert cup with dark chocolate cacao nibs. The peanut butter was replaced by tahini, and the sugar was replaced by dates in the control and variant, respectively. Proximate analyses for the nutritional content of both dessert cups was collected. Analyses included: Total cal/g using bomb calorimetry, antioxidant potential by a ferric reducing ability of plasma (FRAP), Soxhlet for lipid determination, kjeldahl for protein determination, and fiber via a ANKOM Fiber Analyzer. Results: Calories for the control yielded 5961 cal/g, and the variant, 6007.5 cal/g. The absorbance data for FRAP was 2.9996 and 4.5426, for the control and variant respectively. Lipid content was 46.65% for the control (% Ether Extract (Crude Fat)) and 46.9% for the variant (% Ether Extract (Crude Fat)). Protein content for the control was 6.25%, and 9.65% for the variant. Analysis for dietary fiber found insoluble dietary fiber to be 26.6% and soluble dietary fiber 0% for the control. The variant’s insoluble dietary fiber content was 21.4% and soluble dietary fiber 8.7%. Finally, dry matter was 98.6% for the control, and 97.4% for the variant. Conclusion: Data collected showed the greatest differences between antioxidants, fiber, and protein, with the variant having the highest percent content of each nutrient. This research has shown that a dessert alternative can support patients undergoing cancer therapies through the provision of necessary calories and antioxidants. Future research is needed to compare the specific fatty acid content of these two products

No abstract / Mini Dissertation (MPhil)--University of Pretoria, 2019. / Public Law / MPhil / Unrestricted

Les nanoparticules (NPs) métalliques ont de nombreuses applications en catalyse. Certaines d’entre elles (or, argent, cuivre) présentent une absorption dans le visible résultant de l’excitation du plasmon de surface par un champ électromagnétique extérieur. Nous proposons dans ce projet de coupler les propriétés catalytiques de nanoparticules à base d’or avec leurs propriétés de résonance de plasmon de façon à assister la réaction catalytique notamment par l’effet thermique qui en découle. Cette approche de catalyse assistée par plasmon, est générale et peut être utilisée pour une variété de procédés catalytiques exothermiques et endothermiques impliquant des nanoparticules. Cette catalyse assistée par plasmon permettra de réaliser des réactions catalytiques à moindre coût énergétique sous lumière solaire. / Metallic nanoparticles (NPs) have many applications in catalysis. Some of them (gold, silver, copper) have a visible absorption resulting from the excitation of the surface plasmon by an external electromagnetic field. In this project, we propose to couple the catalytic properties of gold-based nanoparticles with their plasmon resonance properties in order to assist the catalytic reaction, in particular by the resulting thermal effect. This plasmon-assisted catalysis approach is general and can be used for a variety of exothermic and endothermic catalytic processes involving nanoparticles. This plasmon-assisted catalysis will make it possible to carry out catalytic reactions at lower energy cost under solar light.

Suite aux premiers travaux réalisés par Ito, Hayashi, Unimoto et Hashmi à la fin du siècle dernier, de nombreux groupes de recherche à travers le monde ont contribué à l’important développement de la catalyse homogène à l’or. Ce dernier, possédant une activité catalytique unique, donne accès à un bon nombre de nouvelles synthèses de composés, jusque-là inaccessible en utilisant d’autres méthodes.Les ynamides, un sous-groupe d’alcynes hétéro-substitués, sont des intermédiaires de synthèse ayant une réactivité et une stabilité modulable. Ils trouvent leur application dans des réactions telles que les additions, les cycloadditions et les cycloisomérisations.Dans ce manuscrit sont présentés deux travaux impliquant des réactions d’ynamides en présence d’un catalyseur à l’or.1) Réarrangement d’éthers de propargyliques d’ynamides catalysé par l’or (I) : Un accès pratique aux allénamides substitués.Les allénamides sont des composés qui présentent de nombreuses applications, d’où l’engouement présent pour accéder à ces composés. Nous avons montré que des allénamides substitués et fonctionnalisés sont facilement accessibles par une réaction de transfert d’hydrure [1,5] suivi d’une fragmentation, le tout catalysé par de l’or et en utilisant des ynamides comme substrats.Notre méthode est rapide et pratique. En effet, la réaction se fait dans des conditions douces (température ambiante) avec une charge catalytique faible (4 mol% de catalyseur à l’or) et donne d’excellents rendements (jusqu’à 99%). En plus d’une bonne compatibilité fonctionnelle sur le carbone terminal (R1 et R2), notre méthode tolère aussi des substituants azotés variés (R’ et R’’). De plus, d’autres transformations in-situ sur les allénamides formés in-situ ont été effectuées. Quelques composés spiros et diènes interessants ont été obtenus avec des rendements excellents.2) Catalyse duale à l’or : Une synthèse originale de dérivés tertahydroquinolines par un mécanisme formel d’addition [4+2]Bien qu’une vaste majorité de la catalyse à l’or contient une activation du système π d’une liaison multiple par un seul complexe d’or, des innovations récentes mettant en jeu deux atomes d’or sur une seule molécule ont été développées par plusieurs groupes, dont le nôtre.Le cycle catalytique est initié par la formation de l’acétylénure d’or et par la coordination d’un autre complexe d’or de la liaison triple de l’ynamide. Après une attaque nucléophile de l’acétylenure d’or sur l’ynamine, un vinylidène d’or est formé. Ce dernier est piégé par la double liaison, donnant naissance au cycle aromatique. / General introductionSince the pioneering work by Ito, Hayashi, Unimoto and Hashmi in late of last century, homogeneous gold catalysis has witnessed tremendous development by contributions from research groups all over the world. Gold catalysts, possessing unique catalytic reactivity, intrigued a large number of novel approaches to target molecules which cannot be accessed by other methodology. Ynamide, which belongs to a subclass of hetero-substituted alkynes, represents a versatile building block with balanced reactivity and stability and found a series of applications in useful transformations, such as additions, cycloadditions and cycloisomerizations.As part of our ongoing interest in gold catalysis and ynamide chemistry, in this manuscript, two works involving ynamide in the presence of gold catalyst was presented:1). Gold(I)-Catalyzed Rearrangement of Propargyl Ethers of ynamides: A Practical Method for the synthesis of Substituted AllenamidesAllenamides are versatile synthetic building blocks that have seen numerous applications and therefore great efforts have been devoted to the access to such compounds. We have shown that a series of substituted and functionalized allenamides were easily accessible via a gold catalysted 1,5-hydride shift/fragmentation sequence using ynamides as the starting material. Our method is rapid and practical. It can be performed under very mild conditions (room temperature) with low catalyst loading (4% gold catalyst) and gave excellent yields (up to 99% yield). Besides the good functionality compatibility in the carbon terminal (R1 and R2), our method also tolerate variuous Nitrogen substituents (R’ and R’’). Moreover, further transformation using in-situ formed allenamides was achieved. Some interesting spiral and diene compounds were also formed in excellent yield.2). Dual gold catalysis: a unique approach to derived-tetrahydroquinolines by a formal [4+2] pathwayAlthough vast majority of gold catalysis features π-activation of a multiple bond by a single gold complex, recent innovative advance involving two gold centers in one single molecule was disclosed recently by several research groups and also by our group.The catalytic cycle was initiated by the formation of gold acetylide and coordination of another gold complex to the triple bond of ynamide. After nucleophilic attack of gold acetylide onto ynamide, gold vinylidene was generated. The formed gold vinylidene was then trapped by double bond, giving rise to aromatic rings.

Cette thèse décrit le développement de nouvelles méthodes de catalyse à l’or et au cuivre pour la synthèse de composés hétérocycliques et de produits trifluorométhylés.Dans un premier temps, une synthèse d’allènes trifluorométhylés par catalyse à l’or a été développée, dont l’étape clé est un transfert d’hydrure 1,5. Cette méthode donne accès de manière efficace et sélective à une large gamme d’allène perfluoroalkylés dont le potentiel synthétique a également été démontré.Le pouvoir catalytique de l’or a alors été utilisé dans une synthèse de 2H-1,3-oxazines reposant sur une cyclisation de type 6-endo d’azido alcynes. Cette méthode donne accès dans des conditions très douces à une gamme sans précédent d’oxazines polysubstituées avec d’excellents rendements.Dans un dernier temps, une méthode d’hydrofonctionnalisation radicalaire d’alcènols catalysée au cuivre. La stratégie impliquée repose sur une abstraction d’hydrogène 1,5, dans laquelle un groupement benzyloxy joue le rôle de donneur d’hydrogène. / This manuscript presents the development of gold- and copper-catalyzed methods for the synthesis of heterocyclic compounds and trifluoromethylated products.Firstly, a gold-catalyzed synthesis of trifluoromethyl allenes was developed, relying on a 1,5 hydride shift. This method allows to access, in a very efficient and selective way, a large range of perfluoroalkylated allenes, of which the synthetic potential was also demonstrated.Afterwards, the catalytic power of gold was then used in a synthesis of 2H-1,3-oxazines, relying on a 6-endo type cyclization of azide-yne substrates. This methods allows to access, in very mild condition, an unprecedently large range of polysubstituted oxazines in excellent yields.Finally, a method for the copper-catalyzed radical hydrofunctionalization of alkenols was developed. The strategy involved relies on a 1,5 hydrogen abstraction, in which a benzyloxy moiety plays the role of the hydrogen donor.

First, this study argues that the Oregon Writers' Project cannot be used as a measurement for the effectiveness of government subsidy of the arts. The people who ran the program never claimed to be supporting art but to be supporting unemployed writers. In fact, the administrators tried to discourage any freedom or flexibility which would have provided a climate for the writer to flourish in the artistic sense. With this recognition in mind, one may not validly use the Writers' Project as a tool for accurate measurement of governmental subsidization of art. This study also takes major exception to a previous work presented on the Federal Writers' Project in the Pacific Northwest. That study argued that a project was unnecessary in the Pacific Northwest due to the area's "literary and intellectual backwardness." In Oregon the program certainly had its problems, but the project was generally successful in meeting the major intent of the program--employing the unemployed in their self-selected profession. This program was not only useful but also humane; furthermore, it managed to preserve important history and the skills of people out of work in a time of severe depression.

A one dimensional, steady flow, unsteady temperature model is used to evaluate the effects of two U.S. Army Corps of Engineers (COE) dams and resulting reservoirs on hourly water temperatures of the mainstem McKenzie River from Delta Park (RM 62.1) to Leaburg Dam (RM 38.8). Both COE projects are on tributaries to the McKenzie River and at present have only bottom withdrawl capabilities.

This work on Marquam Hill area in Portland, a relatively undeveloped urban hillside area, is a pilot study in which environmental factors are evaluated quantitatively in order to delineate limitations on development. The study was undertaken at the request of and in cooperation with the City of Portland Planning Commission and with the State of Oregon Department of Geology and Mineral Industries. Factors considered include various aspects of the land, vegetation and attitudes of inhabitants. Findings are not intended to satisfy need for individual site studies by qualified experts but should show where that expertise is needed. Field data were collected on site by observations, borings, personal interviews and by geophysical surveys; laboratory tests were made on soil samples; studies were compiled of topographic maps and aerial photographs; and pertinent data from available previous works were incorporated. Data were integrated into a series of environmental factor maps including ground slope, bedrock and soil, bedrock structure, soil thickness, ground stability, hydrology, and vegetation. Land use constraints and environmental limitations were defined using u.s. Department of Agriculture, Soil Conservation Service, soil suitability and limitations criteria as a guide. Mapped geologic and environmental constraints were overlayed with the mapped soil criteria to identify areas by limitations. An interpretive map and chart show that most of the study area is moderately to severly limited for most land uses. Some small areas can be considered as slightly limited, but the majority of these are already developed. The constraints are so severe that most of the area should be left in open space. The major recommendation is that any development must be carefully controlled, utilizing stringent grading codes (such as Chapter 70 of the Uniform Building Code) and professional expertise to assure the safety and environmental compatibility of the site. It is suggested that planned unit development, in the form of clustered or low- to medium-rise structures would optimize design for natural conditions, siting locations, and residential density least affecting the surrounding, naturally vegetated, hazardous slopes.

Program evaluation is in its infancy at the Washington County Mental Health Program; it is only within the last two years that there has been any emphasis placed on evaluation activities. The first chapter in this practicum will identify and provide a context for the recent introduction of the management by objectives approach to process evaluation within the Washington County Mental Health Program as well as present a rationale for such an approach; the second chapter in this practicum is a presentation of results obtained from the first follow-up study to employ management objectives as an evaluation tool; the third chapter explores problems inherent in the nature and design of this type of evaluation procedure as well as program implications concerning the utility of results obtained from the study and recommendations for change in both approach and procedure.

A water budget model was developed to estimate year-end lake volumes of Goose Lake, Oregon-California, to determine whether an accurate reconstruction of lake volumes/levels could be made with several synthesized or partial volumetric components. Components evaluated were the lake level/volume observations, precipitation, streamflow, and evaporation during the data-rich study period, 1946 to 1975. By regressing estimated year-end volumes against actual volumes (using actual volumes as the input at the beginning of each year) a correlation coefficient of 0.97 was obtained. By letting the series' year-end volumes be substituted for the following years' antecedent volumes a systematic error was created, identical in time and degree to irrigation consumptive use in the basin. The consideration of this additional component improved the self-generating series. The interaction of the components described by the model was then fed into a reconstruction model which used regression equations relating precipitation and runoff to annual tree-ring width indices. In this manner, a long-term synthetic runoff and precipitation record was developed for the basin for the period 1422 to 1964. Trends in the model output for the recent period (1830 to present) closely parallel recorded observations of lake level/volume although the range of reconstructed volumes was not as extreme as actually occurred. Nevertheless, the "actual" versus "synthesized" lake level series (1946 to 1964) were fairly well correlated (r=0.75), being significant to the 0.99 level. The study shows that tree rings are useful in the reconstruction of hydrologic and climatologic phenomena and are especially sensitive to changes in available water supply but do not show the high interannual variation seen in both precipitation and streamflow. Additionally, the tree ring record appears to be more sensitive to drought than to dry conditions in the basin and is therefore not well suited to determining the recurrence interval of high-water conditions.