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Urocanic acid as an efficient hydroxyl radical scavenger: a quantum theoretical study

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Abstract

The photoisomerization of urocanic acid (UCA)—which is present in human skin epidermis, where it acts as a sunscreen—from its trans isomer to its cis isomer upon exposure to UV-B radiation is known to cause immunosuppression. In recent years, the antioxidant properties of UCA (it acts as a hydroxyl radical scavenger) have also been recognized. In view of this, the mechanisms of stepwise reactions of trans-UCA with up to four hydroxyl radicals were investigated. The molecular geometries of the different species and complexes involved in the reactions (reactant, intermediate and product complexes, as well as transition states) were optimized via density functional theory in the gas phase. Solvation in aqueous media was treated with single point energy calculations using DFT and the polarizable continuum model. Single point energy calculations in the gas phase and aqueous media were also carried out using second-order Møller–Plesset perturbation theory (MP2). The AUG-cc-pVDZ basis set was employed in all calculations. Corrections for basis set superposition error (BSSE) were applied. Vibrational frequency analysis was performed for each optimized structure to ensure the validity of the optimized transition states. It was found that the binding of the first OH· radical to UCA involves a positive energy barrier, while subsequent reactions of OH· radicals are exergonic. Transition states were successfully located, even in those cases where the barrier energies were found to be negative. The cis–trans isomerization barrier energy of UCA and that of the first OH· radical addition to UCA are comparable, meaning that both processes can occur simultaneously. It was found that UCA could serve as an antioxidant in the form of an efficient OH· radical scavenger.

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Acknowledgments

The authors are thankful to the Council of Scientific and Industrial Research (New Delhi) and the University Grants Commission (New Delhi) for financial support.

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  1. Department of Physics, Banaras Hindu University, Varanasi, 221 005, India

    Saumya Tiwari & Phool Chand Mishra

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  1. Saumya Tiwari
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Correspondence to Phool Chand Mishra.

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Fig. SI1

Addition reactions of the second OH· radical at the C2, C4, C6 and C7 sites of C5.OH· (adduct of urocanic acid). ZPE- and BSSE-corrected barrier and released energies (kcal/mol) obtained in aqueous media at the MP2/AUG-cc-pVDZ level of theory using the geometries optimized at the BHandHLYP/AUG-cc-pVDZ level in the gas phase are given near the arrows (DOC 882 kb)

Fig. SI2

Addition reactions of the second OH· radical at the C2, C4 and C5 sites of C6.OH· (adduct of urocanic acid). ZPE- and BSSE-corrected barrier and released energies (kcal/mol) obtained in aqueous media at the MP2/AUG-cc-pVDZ level of theory using the geometries optimized at the BHandHLYP/AUG-cc-pVDZ level in the gas phase are given near the arrows (DOC 873 kb)

Fig. SI3

Addition reactions of the second OH· radical at the C2, C4 and C5 sites of C7.OH· (adduct of urocanic acid). ZPE- and BSSE-corrected barrier and released energies (kcal/mol) obtained in aqueous media at the MP2/AUG-cc-pVDZ level of theory using the geometries optimized at the BHandHLYP/AUG-cc-pVDZ level in the gas phase are given near the arrows (DOC 799 kb)

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Tiwari, S., Chand Mishra, P. Urocanic acid as an efficient hydroxyl radical scavenger: a quantum theoretical study. J Mol Model 17, 59–72 (2011). https://doi.org/10.1007/s00894-010-0699-3

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