Ellagic acid is a biologically active polyphenol found in numerous fruits and vegetables. However, not many papers dealing with the electrochemical properties and protolytic equilibria of ellagic acid have been published so far. The electro-oxidation mechanism of ellagic acid was studied in methanol aqueous media (1:1, v/v) within the pH range of 1.5-9.0, t = 25 +/- A 1 A degrees C, using cyclic voltammetry on a glassy carbon electrode, and by semiempirical calculations. Results show that oxidation of ellagic acid is a pH-dependent, two-step quasireversible process. The slope of peak 1 indicates the exchange of the same number of electrons and protons within the whole studied pH range; the slope of peak 2 changes with the increase of pH, and three different regions are visible. As protolytic equilibria studies revealed that ellagic acid acts as a diprotic acid in the studied conditions (acidity constants were potentiometrically determined as pK (a1) = 5.42 +/- A 0.01 and pK (a2) = 6.76... +/- A 0.01), it is obvious that the electro-oxidation occurs at the hydroxyl group subjected to dissociation. The three different regions are therefore recognized as regions with different dominating species: unionized molecule (H(4)A), monoanion (H(3)A(-)), and dianion (H(2)A(2-)). UV/Vis spectral changes confirmed the proposed equilibria. Heat of formation and electron densities calculated at semiempirical level were used to propose the hydrogen and electron abstraction sites. According to the obtained results, a new mechanism of ellagic acid electro-oxidation is proposed.
TY - JOUR
AU - Simić, Aleksandra Z.
AU - Verbić, Tatjana
AU - Sentić, Milica
AU - Vojic, Mirjana P.
AU - Juranić, Ivan
AU - Manojlović, Dragan
PY - 2013
UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1319
AB - Ellagic acid is a biologically active polyphenol found in numerous fruits and vegetables. However, not many papers dealing with the electrochemical properties and protolytic equilibria of ellagic acid have been published so far. The electro-oxidation mechanism of ellagic acid was studied in methanol aqueous media (1:1, v/v) within the pH range of 1.5-9.0, t = 25 +/- A 1 A degrees C, using cyclic voltammetry on a glassy carbon electrode, and by semiempirical calculations. Results show that oxidation of ellagic acid is a pH-dependent, two-step quasireversible process. The slope of peak 1 indicates the exchange of the same number of electrons and protons within the whole studied pH range; the slope of peak 2 changes with the increase of pH, and three different regions are visible. As protolytic equilibria studies revealed that ellagic acid acts as a diprotic acid in the studied conditions (acidity constants were potentiometrically determined as pK (a1) = 5.42 +/- A 0.01 and pK (a2) = 6.76 +/- A 0.01), it is obvious that the electro-oxidation occurs at the hydroxyl group subjected to dissociation. The three different regions are therefore recognized as regions with different dominating species: unionized molecule (H(4)A), monoanion (H(3)A(-)), and dianion (H(2)A(2-)). UV/Vis spectral changes confirmed the proposed equilibria. Heat of formation and electron densities calculated at semiempirical level were used to propose the hydrogen and electron abstraction sites. According to the obtained results, a new mechanism of ellagic acid electro-oxidation is proposed.
PB - Springer Wien, Wien
T2 - Monatshefte Fur Chemie
T1 - Study of ellagic acid electro-oxidation mechanism
VL - 144
IS - 2
SP - 121
EP - 128
DO - 10.1007/s00706-012-0856-8
ER -
@article{
author = "Simić, Aleksandra Z. and Verbić, Tatjana and Sentić, Milica and Vojic, Mirjana P. and Juranić, Ivan and Manojlović, Dragan",
year = "2013",
abstract = "Ellagic acid is a biologically active polyphenol found in numerous fruits and vegetables. However, not many papers dealing with the electrochemical properties and protolytic equilibria of ellagic acid have been published so far. The electro-oxidation mechanism of ellagic acid was studied in methanol aqueous media (1:1, v/v) within the pH range of 1.5-9.0, t = 25 +/- A 1 A degrees C, using cyclic voltammetry on a glassy carbon electrode, and by semiempirical calculations. Results show that oxidation of ellagic acid is a pH-dependent, two-step quasireversible process. The slope of peak 1 indicates the exchange of the same number of electrons and protons within the whole studied pH range; the slope of peak 2 changes with the increase of pH, and three different regions are visible. As protolytic equilibria studies revealed that ellagic acid acts as a diprotic acid in the studied conditions (acidity constants were potentiometrically determined as pK (a1) = 5.42 +/- A 0.01 and pK (a2) = 6.76 +/- A 0.01), it is obvious that the electro-oxidation occurs at the hydroxyl group subjected to dissociation. The three different regions are therefore recognized as regions with different dominating species: unionized molecule (H(4)A), monoanion (H(3)A(-)), and dianion (H(2)A(2-)). UV/Vis spectral changes confirmed the proposed equilibria. Heat of formation and electron densities calculated at semiempirical level were used to propose the hydrogen and electron abstraction sites. According to the obtained results, a new mechanism of ellagic acid electro-oxidation is proposed.",
publisher = "Springer Wien, Wien",
journal = "Monatshefte Fur Chemie",
title = "Study of ellagic acid electro-oxidation mechanism",
volume = "144",
number = "2",
pages = "121-128",
doi = "10.1007/s00706-012-0856-8"
}
Simić, A. Z., Verbić, T., Sentić, M., Vojic, M. P., Juranić, I.,& Manojlović, D.. (2013). Study of ellagic acid electro-oxidation mechanism. in Monatshefte Fur Chemie
Springer Wien, Wien., 144(2), 121-128.
https://doi.org/10.1007/s00706-012-0856-8
Simić AZ, Verbić T, Sentić M, Vojic MP, Juranić I, Manojlović D. Study of ellagic acid electro-oxidation mechanism. in Monatshefte Fur Chemie. 2013;144(2):121-128.
doi:10.1007/s00706-012-0856-8 .
