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Hydrogen sulfide (H2S) is an endogenously produced signaling gas involved in numerous cellular functions. At the appropriate concentration, exogenous administration of this gasotransmitter regulates vasodilation, promotes angiogenesis of endothelial cells, and generally exhibits beneficial effects as an anti-inflammatory and antioperoxidative agent. H2S is also capable of acting as a gaseous chemotherapeutic agent. Therefore, the therapeutic potential of exogenous delivery of H2S is vast. The delivery of H2S is complicated by its gaseous nature. Under physiologically relevant conditions, H2S is rapidly depleted from solution by oxidation and/or degassing. Therefore, direct exogenous delivery is difficult. To date, most studies have employed Na2S as a convenient H2S source. However, the rapid surge in H2S concentration upon Na2S dissolution followed by its rapid decline poorly mimics the sustained production of low concentrations of H2S that occurs in biological systems. We synthesized a library of S-aroylthiooximes (SATOs)—H2S-releasing compounds that more aptly mimic in vivo H2S concentrations. SATOs are synthesized via reaction of a S-aroylthiohydroxylamine and an aldehyde or ketone. SATOs release H2S in response to a thiol functionality. H2S release from SATOs could be controlled, with H2S release half-lives on the order of minutes to hours. SATO chemistry was utilized to prepare H2S-releasing polymers. Copolymers prepared using RAFT polymerization could be functionalized with SATOs with conversions > 99%, and these polymers released H2S on a similar timescale to our small molecule donors, confirming the viability of SATO formation as a post-polymerization modification strategy. SATO-functionalized polymer amphiphiles were prepared that self-assembled into micelles or vesicles based on their composition. H2S was released from these polymer assemblies more slowly than from the small molecules and statistical polymers. These H2S-releasing micelles were employed in in vitro cytotoxicity studies. H2S released from the micelles was found to be selectively toxic to human colon cancer cells compared with healthy fibroblasts. These polymeric micelle donors outperformed existing H2S donors in terms of their toxicity towards cancer cells. The observed enhanced toxicity was suspected to arise from the slow and sustained release of H2S from the micelles. / Ph. D.

Over the last few decades, the production and consumption of craft beer in the United States has witnessed a spectacular increase. According to the Brewer's Association (2020), there were approximately 89 breweries operating in the United States in 1978 compared to 8,386 in 2019. Along with this rapid market expansion, the cultural status of beer also underwent significant changes. Despite the exponential rise in the number of craft breweries as well as the emergence of a craft beer culture, little empirical scholarship on the field of craft beer exists. In this study, I analyze the rapid status shift of craft beer by exploring its social history of changes that occurred both exogenously to the cultural field of craft beer as well as endogenous developments within the field. Further, I examine in detail the emergence and role of a critical discourse surrounding craft beer culture in relation to its involvement in the elevation of status as well as the construction of symbolic and social boundaries. The theoretical foundation for this study draws on insights from work on cultural fields (Bourdieu 1993), art worlds (Becker 1982), cultural and artistic legitimation (Baumann 2001; 2007a; 2007b; 2011), social and symbolic boundaries (Lamont and Molnar 2002), and the production of culture perspective (Peterson and Anand 2004). Data for this project come both from secondary and original sources including All About Beer magazine and semi-structured face-to-face interviews with craft beer industry professionals. My findings suggest that while the status elevation of the field of craft beer has closely followed those of other legitimized fields (e.g., film), unique discursive and institutional dynamics are also salient. Specifically, I find that through critical discourse, the status elevation of craft beer in the United States context was directly related to a.) the establishment of beer travel as a cultural good, b.) the linkage of craft beer to predominantly white, middle-class leisure activities, c.) the association of beer to other high status gastronomic fields, and d.) the historicization of the field craft beer particularly via the mythologization of early pioneers. / Doctor of Philosophy / Over the last few decades, the production and consumption of craft beer in the United States has witnessed a spectacular increase. According to the Brewer's Association (2020), there were approximately 89 breweries operating in the United States in 1978 compared to 8,386 in 2019. Along with this rapid market expansion, the public perception of craft beer also underwent significant changes. Despite the exponential rise in the number of craft breweries, craft beer's changing status, and the blossoming of American craft beer culture, little empirical scholarship on craft beer exists that explores the sociological aspects of the field. Drawing on multiple sociological theoretical frameworks I employ a multi-method research design to analyze both secondary and original data to explore questions surrounding the upward status elevation of craft beer from 2002 to 2017 in the United States context. My main findings suggest that through critical discourse, the status elevation of craft beer in the United States context was directly related to a.) the establishment of beer travel as a cultural good, b.) the linkage of craft beer to predominantly white, middle-class leisure activities, c.) the association of beer to other high status gastronomic fields such as wine, and d.) the historicization of the field craft beer particularly via the mythologization of early pioneers.

No / Core-shell particles have been prepared by surfactant-free emulsion polymerisations of butyl methacrylate in the presence of either linear or highly branched poly(acrylamidomethylpropane sulphonate)s (L-PAMPS or HB-PAMPS) with dithioate end groups: using a "shell-first" approach. In this method the water soluble PAMPS shells were anchored to the cores by polymerisation of BMA from the chain ends. The linear PAMPS produced non-crosslinked poly(AMPS-BMA) particles but the multiple chain ends of the highly branched PAMPS led to crosslinked particles. The particles were loaded with vascular endothelial growth factor or platelet derived growth factor, both of which are cytokines that are known to be important in the production of new blood vessels. The release of the growth factors was shown to be controlled by the architecture of the shell and we propose a mechanism that involves both ionic interaction of the PAMPS with the heparin-binding domains of the growth factors and size exclusion mediated diffusion.