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Insights into the HO· and HOO· radical scavenging activity of aryl carbamate derivative: a computational mechanistic and kinetic investigation

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Abstract

Aryl carbamates exhibit significant utility due to their diverse range of biological activities, including anticancer, antituberculosis, and antioxidant properties. This study will focus on a comparative evaluation of the antioxidant capabilities of two aryl carbamate derivatives, namely Methyl(Z)-(1-(hydroxyamino) ethyl)-5-(methoxycarbonyl) amino)-2-methyl-1H-indole 1 carboxylate (Compound 1) and Dimethyl (1,3-dioxo-2,3-dihydro-1H-indene-2,2-diyl) bis (4,1 phenylene) dicarbamate (Compound 2). To assess the anti-oxidant capacity, two distinct reactive oxygen species, such as highly reactive hydroxyl (HO·) and moderately reactive hydroperoxyl (HOO·), have been taken into consideration. Four distinct scavenging processes, including RAF, HAT, SETPT, and SPLET, have been investigated here. The RAF mechanism was determined to be the most effective anti-oxidant pathway, regardless of the compounds or free radicals investigated here. For both HO· and HOO·, compound 1 demonstrated more potent scavenging capabilities than compound 2. Compounds 1 and 2 react with the HO· radical very quickly due to its extraordinarily high reactivity; in contrast, the less reactive HOO· provides a rather moderate rate. The calculated values of overall rate constant of Comp. 1 reaction with HOO· are 3.7 × 103 M−1 s−1 (gas phase), 5.3 × 101 M−1 s−1 (water), and 3.6 × 100 M−1 s−1 (pentyl ethanoate). With this context it is clear both of the compounds can work as strong and mild antioxidant against HO· and HOO· radical, respectively.

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Acknowledgements

D. Mandal is very much grateful to the Department of Science and Technology, Government of India, for providing the INSPIRE Faculty Fellowship (DST/INSPIRE/04/2016/001948) and Thapar Institute of Engineering and Technology SEED grant (TU/DORSP/57/7278). C Kaur is thankful to TIET for providing fellowship.

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PES for the reactions of OOH radical, optimized geometry, cartesian coordinate, and thermochemistry of all the species are available in the supplementary information.

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  1. Department of Chemistry and Biochemistry, Thapar Institute of Engineering and Technology, Patiala, Punjab, 147004, India

    Chhinderpal Kaur & Debasish Mandal

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D.M.: Conceptualization, analysis, and Writing- Reviewing and Editing. C.K.: Data calculation, investigation, Writing- initial draft preparation

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Correspondence to Debasish Mandal.

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Kaur, C., Mandal, D. Insights into the HO· and HOO· radical scavenging activity of aryl carbamate derivative: a computational mechanistic and kinetic investigation. Theor Chem Acc 143, 28 (2024). https://doi.org/10.1007/s00214-024-03102-3

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