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Reactions of chlorophyll with hydroxyl radicals via RAF, HAT and SET mechanisms: A theoretical study

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Abstract

To understand the scavenging action of chlorophyll (Chla) found in most of the vegetables towards hydroxyl (\({{\text{OH}}}^{\bullet }\)) radicals, its reactions with \({{\text{OH}}}^{\bullet }\) radicals via RAF, HAT, and SET mechanisms have been investigated theoretically using two layer ONIOM [M06-2X/6-31G(d) (High):M06-2X/3-21G (Low)] method and M06-2X/6–311 + G(d,p) level of density functional theory. The molecular electrostatic potential (MEP), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) plots, HOMO–LUMO energy gap, global hardness (η), global softness (S), electronegativity (χ), and electrophilicity index (ω) of Chla molecule were computed and analyzed to determine its stability and reactive sites. It is found that RAF and HAT reactions are exergonic in both gaseous and aqueous media whereas SET reactions are endergonic in both media. However, all the RAF, HAT and SET reactions studied here are found to be more favourable in aqueous media vs. gas phase. The rate constants of RAF reactions at different sites are found to be of the order of ~ 6.2 × 107–1.8 × 1010 s−1 indicating that RAF reactions would be appreciably fast. This study concludes that chlorophyll can efficiently scavenge \({{\text{OH}}}^{\bullet }\) radicals preferably via RAF and HAT mechanisms and intake of water with chlorophyll can enhance its scavenging actions.

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Acknowledgements

Authors would like to acknowledge the general computational facility of the Department of Physics, Assam University, Silchar, India. Authors would like to thank Dr. María Inés Nicolás-Vázquez for providing coordinate of the chlorophyll molecule for the present study.

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This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

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  1. Department of Physics, Assam University, Silchar, 788011, India

    Swarnadeep Biswas & Pradeep Kumar Shukla

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  1. Swarnadeep Biswas
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S.B. planned, performed simulation, collected data and contributed partly in writing. P.K.S. planned and supervised the research work, analysis of the results and writing of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Pradeep Kumar Shukla.

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11224_2024_2331_MOESM1_ESM.docx

The optimized structures of adducts formed in RAF reactions of Chla and Mchla; Table containing ESP charges of Chla and MChla; reaction free energy and corresponding Boltzmann Populations for Chla and MChla; imaginary frequencies of TSs and tunneling constants; rate constant for the study of RAF involving MChla model; reaction free energies involved in SET mechanism, spin density located at HAT reaction sites, and the Cartesian coordinates of all the optimized TSs involved in RAF for MChla model are provided as Supporting Information. The online version containing supplementary material available at…… (DOCX 10442 KB)

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Biswas, S., Shukla, P.K. Reactions of chlorophyll with hydroxyl radicals via RAF, HAT and SET mechanisms: A theoretical study. Struct Chem (2024). https://doi.org/10.1007/s11224-024-02331-3

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