Thesis (Ph. D.)--University of Oregon, 2002. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 272-280). Also available for download via the World Wide Web; free to University of Oregon users. Address: http://wwwlib.umi.com/cr/uoregon/fullcit?p3055725.

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Yes / Thermally responsive highly branched poly(N-isopropyl acrylamide)s (HB-PNIPAM) were prepared and end-functionalised to give polymers with acid or trihistidine end groups. These polymers exhibit a broad coil-to-globule transition across a wide temperature range which can be measured using covalently attached fluorescent tags. The acid chain ends provided a material with a distinct change in solution behaviour at pH close to the pKa of the carboxylate group. At pH 11 this polymer did not show a cloud point up to 50 °C but fluorescence measurements on the labelled polymers showed that a coil to glubule transition did take place. The globular state, above the LCST, appeared to be more swollen if the end group carried charge then when it was uncharged. A polymer with trihistidine and free carboxylate chain ends, which contained multiple charges at various pH, did show LCSTs at all pH and the polymer globule was shown to be swollen at each pH.

The work presented in this dissertation deals with the development of new methodologies for P-C bond formation as well as synthesizing biologically relevant organophosphorus compounds. A distinct emphasis is given to the important synthetic targets, the H-phosphinates. A review of relevant literature is provided in Chapter 1. Chapter 2 describes the synthesis and structural analyses, of triphenylmethyl-containing phosphorus compounds. For the first time, both phosphonothioic and boranophosphonic acids have been characterized by single X-ray diffractometry. The third chapter details the preparation and the reactivity of phosphine-borane complexes. Novel dialkoxyphosphine-borane complexes were introduced, both as general synthetic intermediates for the preparation of H-phosphinates or disubstituted phosphinic acids, and as boranophosphonate precursors. Related to this chemistry, silylation of an H-phosphinate intermediate can also be conducted and the resulting phosphonite protected with borane. This allows the temporary protection of the sensitive P-H group, so that manipulations of the alkyl chain might be conducted. In chapter 4, the palladium-catalyzed cross-coupling reaction of dialkylphosphites with aryl and heteroaryl halides is presented. An efficient, versatile and economically attractive alternative to the original Hirao cross-coupling by using only 1 mol% (or less) Pd(OAc)2/dppf is described. Moreover, first example of palladium-catalyzed P-C bond formation between activated aryl chlorides and a phosphite are herein reported. Chapter 5 focuses on the free-radical hydrophosphinylation of alkynes. The triethylborane-initiated radical addition of sodium hypophosphite to terminal alkyne affords the previously unknown 1,1-bis-H-phosphinates, precursors of the biologically relevant 1,1-bisphosphonates (e.g., treatment of bone diseases). Thus, the oxidative conversion of 1,1-bis-H-phosphinates to the corresponding bisphosphonates, as well as the synthesis of a series of bio-conjugates (steroids, carbohydrates, fluoroquinolones) was investigated. In the last chapter, the palladium-catalyzed hydrophosphinylation of hypophosphorous acid derivatives to terminal alkynes is reported. In an effort to improve the regioselectivity of the reaction, various terminal alkynes were tested, as well as the solvent and catalyst system.

Introduction: Electronic Nicotine Delivery Systems (ENDS) debuted in 2006 within the U.S market as novel tobacco products and have been gaining popularity since. Without enforced regulations, prevalence of awareness and use has significantly increased. The purpose of this study is to explore the evolving landscape of ENDS using the Host, Agent, Vector, Environment (HAVE) model with a focus on manufactured e-liquids and do it yourself (DIY) e-liquids as the Agent. Methods: Content analysis of e-cigarette web forums was conducted to identify popular brick and mortar point of sales (POS) for the purchase of ENDS products. POS were mapped out within a 1-, 2-, and 3- mile radius from three college campuses using Google Maps. An environmental scan was then conducted on randomly selected POS sites (N=17) where observations on e-liquid flavors and characteristics were identified. In addition, a content analysis of web forums was used to qualitatively characterize DIY e-liquids in depth. Results: A total of 602 flavors were profiled in the POS environmental scans and five main flavor categories of e-liquids were identified: 1) Tobacco and Menthol (16.6%); 2) Desserts and Candies (16.6%); 3) Fruits (20.6%); 4) Drinks (10.1%); 5) Other (36.0%). Most flavored e-liquids were sold in stand-alone vials (91.0%). When sold with manufactured products, flavored e-liquids were sold in E-Hookahs (10.6%) compared to E-Cigarettes (4.7%). Most (96.8%) flavored e-liquids were available with and without nicotine. Based on content analysis of e-cigarette web forums, the words with the highest frequency in the DIY transcripts were: “flavor”, “mixing”, “liquid”, “calculators”, and “nicotine”. Conclusions: Our findings indicate that for both manufactured and DIY e-liquids, flavors are a distinguishing and primary characteristic. Given these findings, increased surveillance efforts to monitor ENDS and e-liquids are necessary to inform regulatory science.

Made available in DSpace on 2014-06-11T19:26:56Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-04-12Bitstream added on 2014-06-13T19:55:23Z : No. of bitstreams: 1 santos_ap_me_sjrp.pdf: 749833 bytes, checksum: 8be58c6f81e3ac600ff8f26430348533 (MD5) / Para todo grupo G infinito, finitamente gerado, pode-se obter para o invariante algébrico end, mais precisamente o número de ends e(G), uma fórmula cohomológica 1-dimensional. O principal objetivo deste trabalho é apresentar, sob certas hipóteses, uma fórmula cohomológica 1-dimensional para o invariante algébrico e(G,H), definido por Scott e Houghton, onde H é um subgrupo de G (Teorema de Swarup). Para tanto, o conceito de subconjunto H-quase invariante de G e resultados como a interpretação do grupo de cohomologia H1(G,M) em termos de derivações (à direita), onde M é um ZG-módulo, e o Lema de Shapiro, são resultados imprescindíveis. Algumas relações desses invariantes com ends de espaços são também apresentadas. / For all infinite group G, finitely generated, one can obtain for the algebric invariant end, more precisely the number of ends e(G), a cohomological 1-dimensional formula. The main objective of this work is to present, under certain hypotheses, a cohomological 1-dimensional formula for the algebric invariant e(G,H), defined by Scott and Houghton, where H is a subgroup of G (Swarup's Theorem). In order to do so, the concept of subset H-almost invariant of G and results like the interpretation of the cohomological group H1(G,M) in terms of derivations (to the right), where M is a ZG-module, and the Shapiro's Lemma, are fundamental results. Some relations of these invariants with space ends are also presented.

Electronic Nicotine Delivery Systems (ENDS) use increases risk of nicotine addiction, impairs brain development, and exposes users to harmful chemicals. Despite these risks, rates of use have been increasing among college student populations. Moreover, family history of addiction (FHA) is a risk factor for substance use disorders. Research has yet to examine the extent FHA has on the risk of ENDS use. The current research examines the effect of FHA on lifetime ENDS use and whether ENDS use is more common in participants with FHA and current alcohol or drug use. Participants (N=2,174) were undergraduates recruited from eight southern universities. Participants were 18 to 24 (Mage=19.25). The sample was 73% female, with the following racial identifications: Caucasian (74.9%), followed by Black/African American (8.8%), Asian (6.7%), multiracial (4.7%), other (3.7%), Middle Eastern (.8%), and American Indian/Alaska Native (.3%). Lifetime ENDS use was measured using the Cigarette and E-Cigarette Use Questionnaire. FHA was measured by participant report of first-degree relatives with a drug or alcohol addiction history. Participant alcohol and drug use were measured via the Alcohol Use Disorders Identification Test and Drug Use Disorders Identification Test. Fifty-five percent of participants had used ENDS products during their lifetime (Mage of first use=13.16, SD=4.63), and 12.5% of the sample reported FHA. A linear regression examined if FHA corresponded with ENDS use. The results were significant, F(1,2158)=10.37, p=.001, R2=.005. FHA significantly predicted ENDS use, β=-0.069, t(2158)=-3.22, p=.001. A chi-square of independence examined the relation between ENDS use and alcohol intake in individuals who disclosed FHA. A significant relation was found, χ2=(1,N=176)=32.20, pχ2=(1,N=176)=9.49, p=.002, with participants who reported no drug use being more likely to engage in ENDS use (86%), compared to those who did report drug use (14%). The present study’s results documented there was a significant negative relation between FHA and ENDS use, such that participants who reported FHA presented decreased ENDS use. These findings are contrary to the literature that documents increased cigarette use among young adults with FHA. In addition, participants who disclosed FHA and current alcohol intake exhibited increased ENDS use. However, the participants who disclosed FHA and current drug use exhibited decreased ENDS use. Our results suggest that future research should examine the extent at which individuals who engage in drug use focus more on their substance of choice rather than ENDS products, as well as investigate other risk behaviors that could impact lifetime ENDS use among this population.

The aim of this work is to show that criticisms of Kantian ethics from the field of virtue ethics misfire because they rely on a widespread reading of Kant which centers on the Groundwork and the Formula of Universal Law as the key elements in his moral philosophy. This reading, I argue, is susceptible both to charges of “empty formalism” and moral “rigorism” as well as the complaint voiced by virtue ethicists that Kantian ethics lacks a full-blooded account of the virtues, along with the attendant desiderata of sociality, character and the emotions. In response, I defend the proposal that the Formula of Humanity and the Doctrine of Virtue in the Metaphysics of Morals represent the final form of Kant’s ethical thought. If this is accurate, a rich and novel ethical theory emerges, and many of the criticisms from the field of virtue ethics are subsequently disarmed.

The aim of this work is to show that criticisms of Kantian ethics from the field of virtue ethics misfire because they rely on a widespread reading of Kant which centers on the Groundwork and the Formula of Universal Law as the key elements in his moral philosophy. This reading, I argue, is susceptible both to charges of “empty formalism” and moral “rigorism” as well as the complaint voiced by virtue ethicists that Kantian ethics lacks a full-blooded account of the virtues, along with the attendant desiderata of sociality, character and the emotions. In response, I defend the proposal that the Formula of Humanity and the Doctrine of Virtue in the Metaphysics of Morals represent the final form of Kant’s ethical thought. If this is accurate, a rich and novel ethical theory emerges, and many of the criticisms from the field of virtue ethics are subsequently disarmed.