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ORIGINAL RESEARCH article

Front. Chem.
Sec. Theoretical and Computational Chemistry
Volume 12 - 2024 | doi: 10.3389/fchem.2024.1486175

Homogenous catalysis of peroxynitrite conversion to nitrate by diarylselenide: A theoretical investigation of the reaction mechanism

Provisionally accepted
Yuan Xue Yuan Xue 1Carrrie Salmon Carrrie Salmon 2Valentin Gogonea Valentin Gogonea 3*
  • 1 The University of Mississippi, University, MS 38677, United States
  • 2 Kent State University, Kent, Ohio, United States
  • 3 Cleveland State University, Cleveland, United States

The final, formatted version of the article will be published soon.

    Quenching peroxynitrite (a reactive oxidant species) is a vital process in biological systems and environmental chemistry, (Radi, 2018, Koppenol, 1999) as it balances redox and mitigates damaging effects in living cells and the environment. Here, we report a systematic analysis on the mechanism of transforming peroxynitrite into nitrate by diarylselenide in water. Through quantum mechanical calculations, this work probes the dynamic isomerization of peroxynitrite in a homogeneous catalytic environment. The mapped potential energy surfaces (PES) of various methods in conjunction with different basis sets suggest that the isomerization mechanism includes four major steps: the reaction of peroxynitrite with diarylselenide via an oxygen-bound selenium, selenium oxidation in the presence of an appropriate oxidant, oxygen transfer and ultimately the generation of nitrate. The molecular orbital analysis suggests a substituent effect in the aromatic ring of diarylselenide for this reaction. Changes in both molecular orbitals and electrostatic potential highlight the significance of the electron transfer step in ensuring the progression of this reaction.

    Keywords: Diarylselenide, peroxynitrite, nitrate, nitrite, reaction mechanism, substituent effect, potential energy surface, Frontier molecular orbitals

    Received: 25 Aug 2024; Accepted: 26 Nov 2024.

    Copyright: © 2024 Xue, Salmon and Gogonea. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) or licensor are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

    * Correspondence: Valentin Gogonea, Cleveland State University, Cleveland, United States

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