The reactivity of dopamine precursors and metabolites towards ABTS•-: an experimental and theoretical study

Dušan Dimić, Dejan Milenković, Zoran Markovic, Jasmina Dimitrić Marković


The antiradical activity of L-3,4-dihydroxyphenylalanine (L-DOPA), dihydroxyphenylacetic acid (DOPAC), homovanillic acid and tyrosine towards ABTS•- was investigated experimentally and theoretically by UV-Vis spectroscopy and DFT theory. The importance of catechol moiety for this reaction was proven due to the formation of intramolecular hydrogen bond in formed anions and radicals. The results indicated L-DOPA and DOPAC as more potent radical scavengers than homovanillic acid and tyrosine just as a consequence of intramolecular hydrogen bond formation. Based on experimental spectra, it was proved that electron transfer led to the reduction of ABTS•-. The values of thermodynamic parameters were used to predict the preferred mechanism. The reaction rates were calculated for the electron transfer processes and it was shown that these were both kinetically and thermodynamically driven processes. Based on the reaction rate values, thermodynamic parameters, and present species, as determined by electronic spectra, it was concluded that Single Proton Loss Electron Transfer (SPLET) is the dominant reaction mechanism in the investigated system.


antioxidant activity; UV-Vis spectroscopy; DFT; radicals

Full Text:

PDF (1,294 kB)


B. Halliwell, J. M. C. Gutteridge, Free Radicals in Biology and Medicine, 3rd ed., Clarendon Press, Oxford, 1999. (

T. L. Lemke, D. A. Williams, V. F. Roche, S. W. Zito, Foye’s principles of medicinal chemistry, Wolters Kluwer Health/Lippincott Williams & Wilkins, 2012. (ISBN 9781451181135)

J. Smythies, Antioxid. Redox Signal. 2 (2000) 575 (

O. Hornykiewicz, Mov. Disord. 17 (2002) 501 (

R. M. Berman, M. Narasimhan, H. L. Miller, A. Anand, A. Cappiello, D. A. Oren, G. R. Heninger, D. S. Charney, Arch. Gen. Psychiatry 56 (1999) 395 (

L. Pauling, Science 160 (1968) 265 (

D. Dimić, D. Milenković, J. Dimitrić Marković, Z. Marković, Phys. Chem. Chem. Phys. 128 (2017) 16655 (

R. L. Prior, X. Wu, K. Schaich, J. Agric. Food Chem. 53 (2005) 4290 (

R. Apak, M. Özyürek, K. Güçlü, E. Çapanoʇlu, J. Agric. Food Chem. 64 (2016) 1028 (

N. J. Christensen, K. P. Kepp, J. Mol. Catal. B Enzym. 100 (2014) 68 (

A. M. Campos, E. A. Lissi, Int. J. Chem. Kinet. 29 (1997) 219 (<219::AID-KIN9>3.0.CO;2-X)

X. Tian, K. M. Schaich, J. Agric. Food Chem. 61 (2013) 5511 (

D. Dimić, D. Milenković, J. D. Marković, Z. Marković, Mol. Phys. (2018) 1166 (

C. Iuga, J. R. Alvarez-Idaboy, A. Vivier-Bunge, J. Phys. Chem. B 115 (2011) 12234 (

R. Álvarez-Diduk, A. Galano, J. Phys. Chem. B 119 (2015) 3479 (

C. Sârbu, D. Casoni, Open Chem. 11 (2013) 679 (

A. Kladna, P. Berczynski, I. Kruk, T. Michalska, A.-E. HY, Luminescence 28 (2013) 450 (

İ. Gülçin, Chem. Biol. Interact. 179 (2009) 71 (

A. Galano, J. Mex. Chem. Soc. 59 (2015) 231 (

R. Re, N. Pellegrini, A. Proteggebte, A. Pannala, M. Yang, C. Rice-Evans, Free Radic. Biol. Med. 26 (1999) 1231 (

T. H. Dunning, J. Chem. Phys. 90 (1989) 1007 (

Y. Zhao, D. G. Truhlar, Theor. Chem. Acc. 120 (2007) 215 (

Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford, CT, 2009 (

A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 113 (2009) 6378 (

J. P. Foster, F. Weinhold, J. Am. Chem. Soc. 102 (1980) 7211 (

NBO 6.0., Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2009

R. Marcus, Rev. Mod. Phys. 65 (1993) 599 (

F. C. Collins, G. E. Kimball, J. Colloid Sci. 4 (1949) 425 (

R. B. Walker, J. D. Everette, J. Agric. Food Chem. 57 (2009) 1155 (

S. L. Scott, W. J. Chen, A. Bakac, J. H. Espenson, J. Phys. Chem. 97 (1993) 6710 (

T. Miura, S. Muraoka, T. Ogiso, Biochem. Pharmacol. 55 (1998) 2001 (

F.-D. Munteanu, C. Basto, G. M. Gübitz, A. Cavaco-Paulo, Ultrason. Sonochem. 14 (2007) 363 (

R. Apak, M. Özyürek, K. Güçlü, E. Çapanoʇlu, J. Agric. Food Chem. 64 (2016) 997 (

O. Erel, Clin. Biochem. 37 (2004) 277 (

Z. Marković, J. Tošović, D. Milenković, S. Marković, Comput. Theor. Chem. 1077 (2016) 11 (

N. Nenadis, L. F. Wang, M. Tsimidou, H. Y. Zhang, J. Agric. Food Chem. 52 (2004) 4669 (


Copyright (c) 2019 J. Serb. Chem. Soc.

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

IMPACT FACTOR 0.797 (139 of 171 journals)
5 Year Impact Factor 0.923 (134 of 171 journals)