Peroxynitrite is a powerful biological oxidant generated in vivo from the reaction between nitric oxide and superoxide. Decomposition of peroxynitrite (ONOO ) occurs through protonation to peroxynitrous acid (ONOOH). Thus, at pH 11-12, peroxynitrite is stable for days; whereas, at pH 7, it has a half-life of approximately 1 sec. The decomposition mechanism has long been associated with free radical generation, yet the formation of free hydroxyl radical during the decomposition of peroxynitrous acid has been shown to be thermodynamically unlikely. Spin trapping using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) has yielded some evidence for the DMPO-OH adduct. another report shows the formation of DMPOX, a further oxidation product of DMPO. We characterized the reaction between ONOO and a novel spin trap, DEPMO. We were unable to detect the DEPMPO-OH adduct. However, when glutathione (GSH) was present, we observed the formation of the DEPMPO-SG adduct. The DEPMPO-SG signal was not affected by the presence of hydroxyl radical scavengers indicating, as has been reported previously, that the mechanism is a direct reaction between ONOO and GSH and does not involve the HO-like activity of ONOO . We are currently investigating the EPR spectra of DEPMPO adducts formed in systems containing acidified nitrite and hydrogen peroxide.

Agency
National Institute of Health (NIH)
Institute
National Center for Research Resources (NCRR)
Type
Biotechnology Resource Grants (P41)
Project #
5P41RR001008-21
Application #
5222117
Study Section
Project Start
Project End
Budget Start
Budget End
Support Year
21
Fiscal Year
1996
Total Cost
Indirect Cost
Mao, Li; Liu, Yu-Xiang; Huang, Chun-Hua et al. (2015) Intrinsic Chemiluminescence Generation during Advanced Oxidation of Persistent Halogenated Aromatic Carcinogens. Environ Sci Technol 49:7940-7
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Li, Yan; Huang, Chun-Hua; Liu, Yu-Xiang et al. (2014) Detoxifying polyhalogenated catechols through a copper-chelating agent by forming stable and redox-inactive hydrogen-bonded complexes with an unusual perpendicular structure. Chemistry 20:13028-33
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Sheng, Zhi-Guo; Li, Yan; Fan, Rui-Mei et al. (2013) Lethal synergism between organic and inorganic wood preservatives via formation of an unusual lipophilic ternary complex. Toxicol Appl Pharmacol 266:335-44
Qin, Hao; Huang, Chun-Hua; Mao, Li et al. (2013) Molecular mechanism of metal-independent decomposition of lipid hydroperoxide 13-HPODE by halogenated quinoid carcinogens. Free Radic Biol Med 63:459-66
Huang, Chun-Hua; Shan, Guo-Qiang; Mao, Li et al. (2013) The first purification and unequivocal characterization of the radical form of the carbon-centered quinone ketoxy radical adduct. Chem Commun (Camb) 49:6436-8
Sheng, Zhi-Guo; Huang, Wei; Liu, Yu-Xiang et al. (2013) Ofloxacin induces apoptosis via ?1 integrin-EGFR-Rac1-Nox2 pathway in microencapsulated chondrocytes. Toxicol Appl Pharmacol 267:74-87
Sheng, Zhi-Guo; Huang, Wei; Liu, Yu-Xiang et al. (2013) Bisphenol A at a low concentration boosts mouse spermatogonial cell proliferation by inducing the G protein-coupled receptor 30 expression. Toxicol Appl Pharmacol 267:88-94
Liddle, Brendan J; Wanniarachchi, Sarath; Hewage, Jeewantha S et al. (2012) Electronic communication across diamagnetic metal bridges: a homoleptic gallium(III) complex of a redox-active diarylamido-based ligand and its oxidized derivatives. Inorg Chem 51:12720-8

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