Antioxidant Activity and Proton Coupled Electron Transfer Processes in Conformationally Restricted Naphthalene peri-Dichalcogenides

Date
2019-08-23
Journal Title
Journal ISSN
Volume Title
Publisher
Abstract
Conformationally restricted naphthalene peri-dichalcogenides are powerful mimetics of the selenoenzyme glutathione peroxidase (GPx), and form charge transfer complexes with the electron acceptor tetracyanoquinodimethane (TCNQ). More recently, the Back group has discovered that these molecules display unusual NMR behaviour. This thesis describes a thorough investigation into this NMR behaviour, which is attributed to a proton-coupled electron transfer process (PCET) between the dichalcogenide and its own conjugate acid to form a radical and a radical cation. Evidence supporting this conclusion comes from NMR experiments, EPR spectroscopy, reversibility with sodium dithionite, as well as computational results. Most conformationally restricted naphthalene peri-diselenides synthesized thus far have poor water solublity, a major limitation to serve as GPx mimetics. The second part of this thesis will describe attempts to alleviate this issue by describing the synthesis and GPx like activity of more polar conformationally restricted naphthalene peri-diselenides.
Description
Keywords
Antioxidant, Selenium, Chemistry
Citation
Tuck, T. A. (2019). Antioxidant Activity and Proton Coupled Electron Transfer Processes in Conformationally Restricted Naphthalene peri-Dichalcogenides (Master's thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.