Theoretical Study of Intramolecular Proton Transfer in Flavonols with Density Functional Theory

Khajadpai Thipyapong, Nuttawisit Yasarawan

Abstract


Intramolecular proton transfer (IPT) reactions of four flavonols. i.e. kaempferol, morin, morin-5*-sulfonate and morin-7-O-sulfate in aqueous solution have been investigated using density functional methods with under polarizable continuum model (PCM). The levels of theory used were B3LYP/6-311++G(d,p) and CAM-B3LYP/6-311++G(d,p). Transition states of reactions were calculated using the QST2 method. For all flavonols tested, the normal form is much more stable than its respective zwitterionic form, due to the marked uniformity of electron density distribution in the molecular structure of the former. The potential for each flavonol to undergo IPT depends considerably on either the strength of intramolecular hydrogen bonding or electronic effect of substituents. The computed thermodynamic and kinetic data altogether manifest that the most and the least favorable IPT reactions belong to morin-7-O-sulfate and kaempferol, respectively.

Keywords :  Density Functional Theory, PCM, proton transfer, flavonols


Full Text:

PDF

References


Alkhamees, O. A. (2013). Morin a flavonoid exerts antioxidant potential in streptozotocin-induced hepatotoxicity. British Journal of Pharmacology and Toxicology 4(1), 10-17.

Becke, A. D. (1993). Density-functional thermochemistry III. the role of exact exchange. Journal of Chemical Physics, 98, 5648-5652.

Bondi, A. (1964). van der Waals Volumes and Radii. Journal of Physical Chemistry, 68, 441-452.

Calderon-Montaño, J. M., Burgos-Moron, E., Perez-Guerrero, C., & Lopez-Lazaro, M. (2011). A review on the dietary flavonoid kaempferol. Mini-Reviews in Medicinal Chemistry, 11(4), 298–344.

Chen, A. Y., & Chen, Y. C. (2013). A review of the dietary flavonoid, kaempferol on human health and cancer chemoprevention. Food Chemistry, 138(4), 2099-2107.

Chen, Y.T., Zheng, R. L., Jia Z. J, & Ju, Y. (1990). Flavonoids as superoxide scavengers and antioxidants. Free Radical Biology & Medicine, 9(1), 19-21.

Doroshenko, A. O., Posokhov, E. A., Verezubova, A. A., & Ptyagina, L. M. (2000). Excited state intramolecular proton transfer reaction and luminescent properties of the ortho-hydroxy derivatives of 2,5-diphenyl- 1,3,4-oxadiazole. Journal of Physical Organic Chemistry, 13(5), 253-265.

Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A., Nakatsuji, H., Li, X., Caricato, M., Marenich, A. V., Bloino, J., Janesko, B. G., Gomperts, R., Mennucci, B., Hratchian, H. P., Ortiz, J. V., Izmaylov, A. F., Sonnenberg, J. L., Williams, Ding, F., Lipparini, F., Egidi, F., Goings, J., Peng, B., Petrone, A., Henderson, T., Ranasinghe, D., Zakrzewski, V. G., Gao, J., Rega, N., Zheng, G., Liang, W., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Throssell, K., Montgomery Jr, J. A., Peralta, J. E., Ogliaro, F., Bearpark, M. J., Heyd, J. J., Brothers, E. N., Kudin, K. N., Staroverov, V. N., Keith, T. A., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A. P., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Millam, J. M., Klene, M., Adamo, C., Cammi, R., Ochterski, J. W., Martin, R. L., Morokuma, K., Farkas, O., Foresman, J. B., Fox, D. J., Gaussian 16 Revision B.01 (2016), Gaussian Inc., Wallingford CT.

Georgieva, I., Trendafilova, N., Aquino, A. J. A., & Lischka, H. (2007). Excited-state proton transfer in 7-hydroxy-4- methylcoumarin along a hydrogen-bonded water wire. Journal of Physical Chemistry A, 111(1), 127–135.

Hirschfelder, J. O., & Wigner, E (1939). Some quantum-mechanical considerations in the theory of reactions involving an activation energy. Journal of Chemical Physics, 7, 616–628.

Jacquemin, D., Perpète, E.A., Scuseria, G.E., Ciofini, I., & Adamo, C. (2008). TD-DFT performance for the visible absorption spectra of organic dyes: conventional versus long-range hybrids. Journal of Chemical Theory and Computation, 4, 123-135.

Laidler, K. J., & King, M. C. (1983). Development of transition-state theory. Journal of Physical Chemistry, 87(15),

-2664.

Lee, C., Yang, W., & Parr, R.G. (1988). Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B, 37, 785-789.

Marenich, A.V., Cramer, C.J., & Truhlar, D.G. (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. Journal of Physical Chemistry B, 113, 6378-6396.

Markovic, Z., Milenkovic, D., Dorovic, J., Markovic, J. M. D., Stepanic, V., Lucic, B., & Amic, D. (2012). Free radical scavenging activity of morin 2′-O-phenoxide anion, Food Chemistry, 135, 2070–2077.

McMorrow, D., & Kasha, M. (1984). Intramolecular excited-state proton transfer in 3-hydroxyflavone: hydrogen- bonding solvent perturbations. Journal of Physical Chemistry, 88(11), 2235–2243.

Panhwar, Q. K. & Memon, S. (2011). Synthesis and evaluation of antioxidant and antibacterial properties of morin complexes. Journal of Coordination Chemistry, 64, 2117-2129.

Parthasarathi, P., & Subramanian, V. (2006). Characterization of hydrogen bonding: from van der Waals interactions to covalency. In. Grabowski, S.J. (Ed.), Hydrogen Bonding - New Insights. (pp. 1-50). Dordrecht: Springer.

Pieniazek, E., Kalembkiewicz, J., Dranka, M., & Woznicka, E. (2014). Syntheses, crystal structures and antioxidant study of Zn(II) complexes with morin-5*-sulfonic acid (MSA). Journal of Inorganic Biochemistry, 141, 180-187.

Sengupta, B., Reilly, S. M., Davis, D. E. Jr, Harris, K., Wadkins, R. M, Ward, D., Gholar, D., & Hampton, C. (2015). Excited state proton transfer of natural flavonoids and their chromophores in duplex and tetraplex DNAs. Journal of Physical Chemistry B, 119(6), 2546-56.

Seyoum, A., Asres, K., & El-Fiky F. K. (2006). Structure–radical scavenging activity relationships of flavonoids. Phytochemistry, 67(18), 2058-2070.

Suwattanamala, A., & Ruangpornvisuti, V. (2009). Isomeric structures of benzimidazole, benzoxazole, and benzothiazole derivatives, their electronic properties and transformations. Structural Chemistry, 20,

-631.

Yanai, T., Tew, D. P., & Handy, N.C. (2004). A new hybrid exchange–correlation functional using the Coulomb- attenuating method (CAM-B3LYP). Chemical Physics Letter, 393, 51-57.

Yasarawan, N., Thipyapong, K., & Ruangpornvisuti, V. (2014). Exploring molecular structures, orbital interactions, intramolecular proton-transfer reaction kinetics, electronic transitions and complexation of

-hydroxycoumarin species using DFT methods. Journal of Molecular Graphics and Modelling, 51,

-26.


Refbacks

  • There are currently no refbacks.