Homogenous catalysis of peroxynitrite conversion to nitrate by diaryl selenide: a theoretical investigation of the reaction mechanism

Yuan Xue; Carrie Salmon; Valentin Gogonea

doi:10.3389/fchem.2024.1486175

Homogenous catalysis of peroxynitrite conversion to nitrate by diaryl selenide: a theoretical investigation of the reaction mechanism

Front Chem. 2024 Dec 16:12:1486175. doi: 10.3389/fchem.2024.1486175. eCollection 2024.

Authors

Yuan Xue^#^{1

2}, Carrie Salmon^#³, Valentin Gogonea^{4

5

6}

Affiliations

¹ Department of Chemistry and Biochemistry, The University of Mississippi, University, MS, United States.
² Department of Chemistry and Biochemistry, Oberlin College and Conservatory, Oberlin, OH, United States.
³ Department of Physics, Kent State University, Kent, OH, United States.
⁴ Department of Chemistry, Cleveland State University, Cleveland, OH, United States.
⁵ Department of Cardiovascular and Metabolic Sciences, Lerner Research Institute, Cleveland Clinic, Cleveland, OH, United States.
⁶ Center for Microbiome and Human Health, Cleveland Clinic, Cleveland, OH, United States.

^# Contributed equally.

Abstract

Quenching peroxynitrite (a reactive oxidant species) is a vital process in biological systems and environmental chemistry as it maintains redox balance and mitigates damaging effects in living cells and the environment. In this study, we report a systematic analysis of the mechanism of transforming peroxynitrite into nitrate using diaryl selenide in water. Through quantum mechanical calculations, we investigate the dynamic isomerization of peroxynitrite in a homogeneous catalytic environment. The mapped potential energy surfaces (PESs) generated using various methods in conjunction with different basis sets suggest that the isomerization mechanism includes four major steps: the reaction of peroxynitrite with diaryl selenide via 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 on the aromatic ring of diaryl selenide in 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: diaryl selenide; frontier molecular orbitals; nitrate; nitrite; peroxynitrite; potential energy surface; reaction mechanism; substituent effect.

Grants and funding

The author(s) declare that financial support was received for the research, authorship, and/or publication of this article. This work was partially supported by the National Institutes of Health grants, P01HL147823, R01DK123236, and R01NS124547, and the Advanced Cyberinfrastructure Coordination Ecosystem: Services and Support (ACCESS) program (supported by the National Science Foundation grants #2138259, #2138286, #2138307, #2137603, and #2138296) through allocation MCB170023. YX and CS acknowledge the computational grants, POBC0041 and PWOO0015, and the support from the Ohio Supercomputer Center. YX acknowledges the SEC Emerging Scholar Distinguished Postdoctoral Fellowship from the University of Mississippi during the Academic Year 2023–2024.