The reactive nitric oxide species (RNOS) nitroxyl (HNO) has exhibited both beneficial and deleterious biological effects. In particular, HNO autoxidation can lead to harmful modifications of biomolecules, yet the products of HNO/O₂ remain undetermined. A conceivable product is peroxynitrous acid (ONOOH), however a comparison of the chemistry of HNO/O₂ to synthetic peroxynitrite (ONOO⁻) determined that these RNOS have distinct reactive profiles. This study compares the reactivity of HNO and NO⁻ in the presence of O₂ to synthetic ONOO⁻ and the autoxidation of HNO at high pH (NO⁻/O₂) in an effort to shed light on the products of HNO autoxidation. All species exhibited the capacity for two-electron oxidation, but differences between ONOO⁻ and NO⁻/O₂ and HNO/O₂ were observed in terms of one-electron oxidation, hydroxylation, nitration and buffer effects. NO⁻/O₂ exhibited a reactive profile similar to ONOO⁻, suggesting that protonation of ONOO⁻leads to a unique species from the autoxidation of HNO.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/228472 |
| Date | January 2012 |
| Creators | Buttitta, Lisa Ann |
| Contributors | Miranda, Katrina M., Lichtenberger, Dennis L., Montfort, William R., Miranda, Katrina M. |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | English |
| Detected Language | English |
| Type | text, Electronic Thesis |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
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