A quantum chemical study on the reactivity of four licorice flavonoids scavenging ·OOCl3C

Abstract

Isoliquiritigenin, liquiritigen, uralenol, and neouralenol are four natural licorice flavonoid compounds extracted from licorice, which have the ability of scavenging free radicals. In this paper, the density functional theory (DFT) was used to study the microscopic reaction mechanism of the four kinds of licorice flavonoids respectively scavenging ·OOCl3C in vivo. At the level of M06-2X/6-311+G(d,p), the geometries of all stationary points for hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways were optimized. The thermodynamic parameters and kinetic parameters of each reaction pathway were obtained, and the potential energy surface information of each reaction pathway was obtained too. Using the continuum solvation model based on solute electron density (SMD), the influence of the solvation effect on the reaction was calculated. The main mechanisms and reactive sites for the capture of ·OOCl3C by four licorice flavonoids, liquiritigen, isoliquiritigenin, uralenol, and neouralenol, were determined. Research indicates liquiritigen captures ·OOCl3C by HAT mechanism. The HAT pathway on the B′ ring of liquiritigen is the main reactive site. Isoliquiritigenin captures ·OOCl3C in the body through HAT and RAF mechanism. The RAF pathway is the dominant reaction pathway. The C1 site on the carbon–carbon double bond linking the two benzene rings is the main reactive site. Uralenol and neouralenol capture ·OOCl3C by HAT mechanism. The main reactive site of uralenol is B6 site, and the main reactive site of neouralenol is B′ 2 site. By this study, the potential energy surface information difficult to capture by experimental research is obtained, which provides a reliable theoretical basis for the further screening of highly active natural free radical scavengers of flavonoids in licorice and provides the support for the improvement of the development and application technology of licorice.

This is a preview of subscription content, log in to check access.

Fig. 1
Scheme 1
Scheme 2
Fig. 2
Scheme 3
Scheme 4
Fig. 3

References

  1. 1.

    Labatrobert J, Robert L (2014) Longevity and aging. Role of free radicals and xanthine oxidase. A review [J]. Pathol Biol 62:61–66

    Article  CAS  Google Scholar 

  2. 2.

    Yin F, Sancheti H, Patil I, Cadenas E (2016) Energy metabolism and inflammation in brain aging and Alzheimer’s disease[J]. Free Radic Biol Med 100:108–122

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. 3.

    Connor HD, Therman RG, Galiza MD, Mason RP (1986) The formation of a novel free radical metabolite from CCl4 in the perfused rat liver in vivo[J]. J Biol Chem 261:4542–4548

    CAS  PubMed  Google Scholar 

  4. 4.

    Linton A, Goebl M, Fagan NK (1985) Free radical one-electron versus hydroxyl radical-induced oxidation. Reaction of trichoromethylperoxyl radicals with simple and substituted aliphatic sulphides in aqueous solution[J]. Cheminform 16:647–651

    Google Scholar 

  5. 5.

    Miao JL, Wang WF, Pan JX, Han Z, Yao S (2001) Pulse radiolysis study on the mechanisms of reactions of CCl3OO· radical with quercetin, rutin and epigallocatechin gallate[J]. Sci China (Ser B) 44:353–359

    Article  CAS  Google Scholar 

  6. 6.

    Zhao WN, Yao SD, Wang Q, Qian S, Wang W, Han Y (2003) Reaction of carotenoids with CCl3OO· by using pulse radiolysis[J]. Sci China (Ser B) 46:57–62

    CAS  Google Scholar 

  7. 7.

    Tang RZ, Zhang P, Li HX, Liu YC, Wang WF (2011) Pulse radiolysis study of the reactions between phenothiazine and CCl3OO·, ·OH [J]. Acta Phys -Chim Sin 27:1975–1197

    CAS  Google Scholar 

  8. 8.

    Dong Y, Zhao M, Zhao T, Feng M, Chen H (2014) Bioactive profiles, antioxidant activities, nitrite scavenging capacities and protective effects on H2O2-injured PC12 cells of Glycyrrhiza Glabra L. leaf and root extracts[J]. Molecules 19:9101–9113

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  9. 9.

    Wang J, Zhang J, Gao W, Wang Q, Yin SS, Liu H, Man SL (2013) Identification of triterpenoids and flavonoids, step-wise aeration treatment as well as antioxidant capacity of Glycyrrhiza Uralensis Fisch. cell[J]. Ind Crop Prod 49:675–681

    Article  CAS  Google Scholar 

  10. 10.

    Asha MK, Debraj D, Dethe S, Bhaskar A, Muruganantham N, Deepak M (2017) Effect of flavonoid-rich extract of Glycyrrhiza Glabra on gut-friendly microorganisms, commercial probiotic preparations, and digestive enzymes[J]. J Nutraceuticals Funct Med Foods 14:323–333

    CAS  Google Scholar 

  11. 11.

    Kang XF, Li HL, Wang WQ (2016) Evaluation of the antioxidant activity of fat-soluble flavonoids in aerial parts of Glycyrrhiza Uralensis Fisch[J]. Global Traditional Chin Med 9:567–570

    Google Scholar 

  12. 12.

    Yang R, Yuan BC, Ma YS, Zhou S, Zhang HZ, Liu JY, Li WD, Liu Y (2016) Simultaneous determination of liquiritin, isoliquiritin, liquiritigenin and isoliquiritigen in Glycyrrhiza Uralensis Fisch., Glycyrrhiza Glabra L. and Glycyrrhiza Inflata Bat. by HPLC.[J]. Chin J Pharm Anal 36:1729–1736

    Google Scholar 

  13. 13.

    Jia SS, Ma CM, Wang JM (1990) Studies on flavonoid constituents isolated from the leaves of Glycyrrhiza uralensis Fisch. [J]. Acta Pharm Sin 25:758–762

    CAS  Google Scholar 

  14. 14.

    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr J-A, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09 (Revision A. 02). Gaussian Inc., Wallingford

    Google Scholar 

  15. 15.

    Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Accounts 120:215–241

    Article  CAS  Google Scholar 

  16. 16.

    Garzón A, Bravo I, Barbero AJ, Albaladejo J (2014) Mechanistic and kinetic study on the reactions of coumaric acids with reactive oxygen species: a DFT approach. J Agric Food Chem 62:9705–9710

    Article  CAS  PubMed  Google Scholar 

  17. 17.

    Galano A, Alvarez-Idaboy JR (2014) Kinetics of radical-molecule reactions in aqueous solution: a benchmark study of the performance of density functional methods. J Comput Chem 35:2019–2026

    Article  CAS  PubMed  Google Scholar 

  18. 18.

    Marković S, Tošović J (2016) Comparative study of the antioxidative activities of caffeoylquinic and caffeic acids. Food Chem 210:585–592

    Article  CAS  PubMed  Google Scholar 

  19. 19.

    Marenich AV, Cramer CJ, Truhlar DG (2009) Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem B 113:6378–6396

    Article  CAS  PubMed  Google Scholar 

  20. 20.

    Okuno Y (1997) Theoretical investigation of the mechanism of the baeyer-villiger reaction in nonpolar solvents. Chem Eur J 3:212–218

    Article  CAS  PubMed  Google Scholar 

  21. 21.

    Benson SW (1982) The foundations of chemical kinetics. RE Krieger, Malabar

    Google Scholar 

Download references

Acknowledgments

We thank the grid computing server provided by the Chinese Academy of Sciences.

Funding

This work is supported by the National Basic Research Program of China (2012CB723308), the National Natural Science Foundation of China (51337002 and 50977019), the Doctoral Foundation by the Ministry of Education of China (20112303110005), and the Science Foundation for Distinguished Young Scholar of Heilongjiang Province (JC201206).

Author information

Affiliations

Authors

Corresponding author

Correspondence to Hui Zhang.

Ethics declarations

Competing interests

The authors declare that they have no competing interests.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOC 1257 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wang, A., Lu, Y., Du, X. et al. A quantum chemical study on the reactivity of four licorice flavonoids scavenging ·OOCl3C. Struct Chem 30, 1795–1803 (2019). https://doi.org/10.1007/s11224-019-01312-1

Download citation

Keywords

  • Licorice flavonoids
  • Radical
  • Potential energy surface
  • Quantum chemical