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Updated: Sep 22, 2025

Detection of Nitric Oxide and Superoxide Radical Anion by Electron Paramagnetic Resonance Spectroscopy from Cells using Spin Traps
Published on: August 18, 2012
NO Generation from the Cross-Talks between Ene-diol Antioxidants and Nitrite at Metal Sites
Shourya Gupta1, Swathy Vijayan1, Jeffery A Bertke2
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM), Thiruvananthapuram 695551, India.
Abstract:
The one-electron reduction of nitrite (NO2-) to nitric oxide (NO) and ene-diol oxidation are two important biochemical transformations. Employing mononuclear cobalt-nitrite complexes with CoIII and CoII oxidation states, [(Bz)CoIII(nitrite)2](ClO4) (1) and [(Bz)CoII(nitrite)](ClO4) (2), this report illustrates NO release coupled to stepwise oxidation of ene-diol antioxidants such as l-ascorbic acid (AH2) and catechol. Analysis of the AH2 end-product reveals that the reaction with complex 1 affords dehydroascorbic acid. Intriguingly, a controlled oxidation of AH2 with complex 2 results in a [CoII]-bound ascorbyl radical-anion (8). Finally, NO release with the concomitant generation of metal-bound 3,5-di-tert-butyl-semiquinone radical anion from the reactions of 3,5-di-tert-butyl-catechol and [(Bz)MII(nitrite)](ClO4) (2, M = Co; 4, M = Zn) provides mechanistic insights into the cross-talk between nitrite and ene-diols at the metal sites.
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