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Research Articles

Modified quantum mechanical approach for the estimation of single-electron reduction potential of nitroaromatic compounds in aqueous medium

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Pages 153-160 | Received 13 Mar 2023, Accepted 09 May 2023, Published online: 21 May 2023
 

Abstract

The midpoint single-electron reduction potential of nitroaromatic compounds in aqueous medium at pH 7.0 (potential of ArNO2/ArNO2· couple, Em7) frequently determines their therapeutic and/or toxic properties. However, its estimation remains a complex problem. We propose a modified method of Em7 estimation by quantum mechanical calculations, based on the use of the dielectric continuum model together with a certain number of H2O molecules at the vicinity of nitro group. The optimal number of H2O molecules corresponds to a minimal difference between the experimentally determined and calculated values of Em7, and/or the most negative value of calculated Em7. This enabled us to calculate the Em7 values for a number of ArNO2 (n = 19) with the average deviation of 0.027 V from the experimentally determined ones. Apart from nitrobenzene derivatives, the application of this approach for the representatives of nitropyridines, nitrofurans, nitrothiophenes, and nitrothiazoles was demonstrated. In this case, nitroimidazole derivatives are an exception, evidently due to a strong proton accepting properties of N3 atom of their free radicals.

Acknowledgements

The authors are grateful to the Information Technology Research Center of Vilnius University for the use of supercomputer system, Dr. Jonas Šarlauskas (Institute of Biochemistry) for his generous gift of nitroaromatic compounds, and Dr. Mindaugas Lesanavičius for checking the stylistics of the manuscript.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

This work was supported by the European Social Fund (Measure No. 09.33-LMT-K-712, Grant No. DOTSUT-43/09.3.3.-LMT-K71201-0058/LSS-600000-58).

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