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Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies

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Abstract

Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6′-hydroxyflavone (for monohydroxyflavone) and the 5′,6′-, 7,8- and 3′,4′-dihydroxyflavone which the corresponding radical preferable generated at C6′-O•, C8-O• and C4′-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2′,3′- and 5′,6′dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6′-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.

This work suggests that a preferable region of the catechol group in dihydroxyflavones was selective. The 5′,6′-, 7,8-, and 3′,4′-dihydroxyflavone, which had the corresponding radical at C6′-O•, C8-O• and C4′-O•, shows higher potential of H-atom donation than others.

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Acknowledgments

The authors gratefully thank the Thailand Research Fund (RTA5380010) for financial support. The research facilities at the Laboratory for Computational and Applied Chemistry (LCAC) were made available through the generosity of the National Center of Excellence in Petroleum, Petrochemical Technology and Advanced Materials, the Center of Nanotechnology at Kasetsart University, and the National Research University Program. Support and language correction by native speaker provided from the Kasetsart University Research and Development Institute (KURDI) is also acknowledged.

Compliance with Ethical Standards

The manuscript has not been submitted elsewhere.

This study was funded by the Thailand Research Fund (RTA5380010).

Partial support from Laboratory for Computational and Applied Chemistry (LCAC), the Kasetsart University Research and Development Institute (KURDI), the National Center of Excellence in Petroleum, Petrochemical Technology and Advanced Materials, the National Research University Program was facilitated to this work.

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Authors and Affiliations

  1. Institute of Food Research and Product Development, Kasetsart University, Bangkok, 10900, Thailand

    Witcha Treesuwan

  2. Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok, 10900, Thailand

    Songwut Suramitr & Supa Hannongbua

  3. Center of Nanotechnology, Kasetsart University, Bangkok, 10900, Thailand

    Songwut Suramitr & Supa Hannongbua

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  1. Witcha Treesuwan
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  2. Songwut Suramitr
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Correspondence to Witcha Treesuwan.

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Treesuwan, W., Suramitr, S. & Hannongbua, S. Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies. J Mol Model 21, 137 (2015). https://doi.org/10.1007/s00894-015-2669-2

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  • DOI: https://doi.org/10.1007/s00894-015-2669-2

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