Term | Value | Language |
---|---|---|
dc.contributor.advisor | Pluth, Michael | |
dc.contributor.author | Cerda, Matthew | |
dc.date.accessioned | 2020-09-24T17:34:41Z | |
dc.date.issued | 2020-09-24 | |
dc.identifier.uri | https://scholarsbank.uoregon.edu/xmlui/handle/1794/25694 | |
dc.description.abstract | Hydrogen sulfide (H2S) has recently emerged as an important biological signaling molecule involved in a number of key physiological processes. These observations have generated interest in harnessing H2S as a potential therapeutic agent to treat disease states and chronic conditions associated with H2S-based signaling. A mechanistic analysis of these physiological processes reveals the prevalence of H2S and other reactive sulfur species including sulfane sulfur and persulfides. To better understand the biological properties of these reactive sulfur species, chemical tools which provide methods of generating these fleeting species under controlled reaction conditions are needed. Chapter I is a comprehensive review discussing the large library of small molecule H2S donors reported to date and their respective mechanisms of activation. Chapter II describes the discovery of a highly efficient, chemoselective reaction between free cysteine and thionoesters to generate H2S at physiological pH. Chapter III builds upon the findings of Chapter II to provide a tunable method of H2S generation upon treatment of functionalized dithioesters with free cysteine. Chapter IV demonstrates the validity of using synthetic organic polysulfides in the presence of biological thiols to generate H2S through the intermediate formation of persulfides. Chapter V reports the effect of varying sulfane sulfur content in benzyl polysulfides on thiol-mediated H2S release and thebiological activity of these compounds. Chapter VI highlights the use of dithiasuccinoyl protecting groups to improve current methods of H2S generation which function through the intermediate generation of carbonyl sulfide (COS) in the presence of carbonic anhydrase. Building upon growing interest in the potential biological activity of COS, Chapter VII demonstrates the use of a benzobisimidazolium salt for selective detection of COS by UV-Vis and fluorescent spectroscopy. This dissertation includes previously published and unpublished co-authored material. | en_US |
dc.language.iso | en_US | |
dc.publisher | University of Oregon | |
dc.rights | All Rights Reserved. | |
dc.title | Development of Chemical Tools for Studying Reactive Sulfur Species | |
dc.type | Electronic Thesis or Dissertation | |
dc.description.embargo | 2021-02-17 | |
thesis.degree.name | Ph.D. | |
thesis.degree.level | doctoral | |
thesis.degree.discipline | Department of Chemistry and Biochemistry | |
thesis.degree.grantor | University of Oregon |