Abstract
Recent investigations into plant tissues have indicated that the free form of the natural polyphenolic antioxidant, ellagic acid (EA), is much more plentiful than first envisaged; consequently a re-assessment of solvent systems for the extraction of this water-insoluble form is needed. As EA solubility and its UV-Vis spectrum, commonly used for detection and quantification, are both governed by pH, an understanding of this dependence is vital if accurate EA measurements are to be achieved. After evaluating the pH effects on the solubility and UV-Vis spectra of commercial EA, an extraction protocol was devised that promoted similar pH conditions for both standard solutions and plant tissue extracts. The extraction so devised followed by HPLC with photodiode-array detection (DAD) provided a simple, sensitive and validated methodology that determined free EA in a variety of plant extracts. The use of 100 % methanol or a triethanolamine-based mixture as the standard dissolving solvents were the best choices, while these higher pH-generating solvents were more efficient in extracting EA from the plants tested with the final choice allied to the plants’ natural acidity. Two of the native Australian plants anise myrtle (Syzygium anisatum) and Kakadu plum (Terminalia ferdinandiana) exhibited high concentrations of free EA. Furthermore, the dual approach to measuring EA UV-Vis spectra made possible an assessment of the effect of acidified eluent on EA spectra when the DAD was employed.
Acknowledgements
The authors gratefully acknowledge the funding support received from the Rural Industry Research and Development Corporation (RIRDC).
References
Aaby, K., Skrede, G., & Wrolstad, R. E. (2005). Phenolic composition and antioxidant activities in flesh and achenes of strawberries (Fragaria anananassa). Journal of Agricultural and Food Chemistry, 53, 4032–4040. DOI: 10.1021/jf048001o.10.1021/jf048001o">10.1021/jf048001oSearch in Google Scholar
Aguilera-Carbo, A., Augur, C., Prado-Barragan, L., Aguilar, C., & Favela-Torres, E. (2008). Extraction and analysis of ellagic acid from novel complex sources. Chemical Papers, 62, 440–444. DOI: 10.2478/s11696-008-0042-y.10.2478/s11696-008-0042-y">10.2478/s11696-008-0042-ySearch in Google Scholar
Amakura, Y., Okada, M., Tsuji, S., & Tonogai, Y. (2000). High-performance liquid chromatographic determination with photodiode array detection of ellagic acid in fresh and processed fruits. Journal of Chromatography A, 896, 87–93. DOI: 10.1016/s0021-9673(00)00414-3.10.1016/s0021-9673(00)00414-3">10.1016/s0021-9673(00)00414-3Search in Google Scholar
Association of Official Analytical Chemists (1995). Official methods of AOAC international official method 964.22. (14th ed.). Arlington, VA, USA: Association of Official Analytical Chemists International.Search in Google Scholar
Bala, I., Bhardwaj, S., Hariharan, M. N. V., & Kumar, R. (2006). Analytical methods for assay of ellagic acid and its solubility studies. Journal of Pharmaceutical and Biomedical Analysis, 40, 206–210. DOI: 10.1016/j.jpba.2005.07.006.10.1016/j.jpba.2005.07.006">10.1016/j.jpba.2005.07.006Search in Google Scholar
Barch, D. H., Rundhaugen, L. M., Stoner, G. D., Pillay, N. S., & Rosche, W. A. (1996). Structure-function relationships of the dietary anticarcinogen ellagic acid. Carcinogenesis, 17, 265–269. DOI: 10.1093/carcin/17.2.265.10.1093/carcin/17.2.265">10.1093/carcin/17.2.265Search in Google Scholar
Budavari, S. (1996). The Merck index. (12th ed.). Kenilworth, NJ, USA: Merck.Search in Google Scholar
Canals, I., Portal, J. A., Bosch, E., & Rosés, M. (2000). Retention of ionizable compounds on HPLC. 4. Mobile phase pH measurement in methanol/water. Analytical Chemistry, 72, 1802–1809. DOI: 10.1021/ac990943i.10.1021/ac990943i">10.1021/ac990943iSearch in Google Scholar
da Silva Pinto, M., Lajolo, F. M., & Genovese, M. I. (2008). Bioactive compounds and quantification of total ellagic acid in strawberries (Fragaria x ananassa Duch.). Food Chemistry, 107, 1629–1635. DOI: 10.1016/j.foodchem.2007.10.038.10.1016/j.foodchem.2007.10.038">10.1016/j.foodchem.2007.10.038Search in Google Scholar
Exner, T., & Rickard, K. A. (1982). Contact activation by ellagic acid – the concept of soluble activator disputed. Thrombosis Research, 26, 83–89. DOI: 10.1016/00493848(82)90017-2.10.1016/00493848(82)90017-2">10.1016/00493848(82)90017-2Search in Google Scholar
Fredich, J. E. (2005). Titratable activity of acid tastants. In R. E. Wrolstad, T.E. Acree, E. A. Decker, M. H.Penner, D. S. Reid, S. J. Schwartz, C. F. Shoemaker, D. M. Smith., & P. Sporns(Eds.), Handbook of food analytical chemistry (pp. 343–349). Hoboken, NJ, USA: John Wiley & Sons. DOI: 10.1002/0471709085.app1.10.1002/0471709085.app1Search in Google Scholar
Häkkinen, S. H., Kärenlampi, S. O., Mykkänen, H. M., Heinonen, I. M., & Törrönen, A. R. (2000). Ellagic acid content in berries: Influence of domestic processing and storage. European Food Research and Technology, 212, 75–80. DOI: 10.1007/s002170000184.10.1007/s002170000184">10.1007/s002170000184Search in Google Scholar
Hasegawa, M., Terauchi, M., Kikichi, Y., Nakao, A., Okubo, J., Yoshinaga, T., Hiratsuka, H., Kobayashi, M., & Hoshi T. (2003). Deprotonation processes of ellagic acid in solution and solid states. Monatshefte f¨ur Chemie, 134, 811–821. DOI: 10.1007/s0076-002-0552-1.10.1007/s0076-002-0552-1">10.1007/s0076-002-0552-1Search in Google Scholar
Kähkönen, M. P., Hopia, A. I., Vuorela, H. J., Rauha, J. P., Pihlaja, K., Kujala, T. S., & Heinonen, M. (1999). Antioxidant activity of plant extracts containing phenolic compounds. Journal of Agricultural and Food Chemistry, 47, 3954–3962. DOI: 10.1021/jf990146l.10.1021/jf990146l">10.1021/jf990146lSearch in Google Scholar
Konczak, I., Maillot, F., & Dalar, A. (2014). Phytochemical divergence in 45 accessions of Terminalia ferninandiana (Kakadu plum). Food Chemistry, 151, 248–256. DOI: 10.1016/j.foodchem.2013.11.049.10.1016/j.foodchem.2013.11.049">10.1016/j.foodchem.2013.11.049Search in Google Scholar
Landete, J. M. (2011). Ellagitannins, ellagic acid and their derived metabolites: A review about source, metabolism, function and health. Food Research International, 44, 1150–1160. DOI: 10.1016/j.foodres.2011.04.027.10.1016/j.foodres.2011.04.027">10.1016/j.foodres.2011.04.027Search in Google Scholar
Lee, J. H., & Talcott, S. T. (2004). Fruit maturity and juice extraction influences ellagic acid derivatives and other antioxidant polyphenolics in muscadine grapes. Journal of Agricultural and Food Chemistry, 52, 361–366. DOI: 10.1021/jf034971k.10.1021/jf034971k">10.1021/jf034971kSearch in Google Scholar
Lee, J., Dossett, M., & Finn, C. E. (2012). Rubus fruit phenolic research: The good, the bad and the confusing. Food Chemistry, 130, 785–796. DOI: 10.1016/j.foodchem.2011.08.022.10.1016/j.foodchem.2011.08.022">10.1016/j.foodchem.2011.08.022Search in Google Scholar
Maas, J. L., Wang, S. Y., & Galletta, G. J. (1991). Evaluation of strawberry cultivars for ellagic acid content. HortScience, 26, 66–68.10.21273/HORTSCI.26.1.66Search in Google Scholar
Mattila, P., & Kumpulainen, J. (2002). Determination of free and total phenolic acids in plant-derived foods by HPLC with diode-array detection. Journal of Agricultural and Food Chemistry, 50, 3660–3667. DOI: 10.1021/jf020028p.10.1021/jf020028p">10.1021/jf020028pSearch in Google Scholar
Muñoz-Muñoz, J. L., Garcia-Molina, F., Garcia-Molina, M., Tudela, J., Garcia-Canovas, F., & Rodriguez-Lopez, J. N. (2009). Ellagic acid: Characterization as substrate of polyphenol oxidase. Life, 61, 171–177. DOI: 10.1002/iub.143.10.1002/iub.143">10.1002/iub.143Search in Google Scholar
Panichayupakarananta, P., Issuriya, A., Sirikatitham, A., & Wang, S. W. (2010). Antioxidant assay-guided purification and LC determination of ellagic acid in pomegranate peel. Journal of Chromatographic Science, 48, 456–459. DOI: 10.1093/chromsci/48.6.456.10.1093/chromsci/48.6.456">10.1093/chromsci/48.6.456Search in Google Scholar
Pfundstein, B., El Desouky, S. K., Hull, W. E., Haubner, R., Erben, G., & Owen, R. W. (2010). Polyphenolic compounds in the fruits of Egyptian medicinal plants (Terminalia ballerica, Terminalia chebula and Terminalia horrida): Characterisation, quantitation and determination of antioxidant capacities. Phytochemistry, 71, 1132–1148. DOI: 10.1016/j.phytochem.2010.03.018.10.1016/j.phytochem.2010.03.018">10.1016/j.phytochem.2010.03.018Search in Google Scholar
Press, R. E., & Hardcastle, D. (1969). Some physio–chemical properties of ellagic acid. Journal of Applied Chemistry, 19, 247–251. DOI: 10.1002/jctb.5010190903.10.1002/jctb.5010190903">10.1002/jctb.5010190903Search in Google Scholar
Rosés, M., & Bosch, E. (2002). Influence of mobile phase acid-base equilibria on the chromatographic behavior of protolytic compounds. Journal of Chromatography A, 982, 1–30. DOI: 10.1016/s0021-9673(02)01444-9.10.1016/s0021-9673(02)01444-9">10.1016/s0021-9673(02)01444-9Search in Google Scholar
Sakulnarmrat, K., & Konczak, I. (2012). Composition of native Australian herbs polyphenolic-rich fractions and in-vitro inhibitory activities against key enzymes relevant to metabolic syndrome. Food Chemistry, 134, 1011–1019. DOI: 10.1016/j.foodchem.2012.02.217.10.1016/j.foodchem.2012.02.217">10.1016/j.foodchem.2012.02.217Search in Google Scholar
Sanli, N., Fonrodona, G., Barrón, D., Özkan, G., & Barbosa, J. (2002). Prediction of chromatographic retention pKa values and optimization of the separation of polyphenolic acids in strawberries. Journal of Chromatography A, 975, 299–309. DOI: 10.1016/s0021-9673(02)01113-5.10.1016/s0021-9673(02)01113-5">10.1016/s0021-9673(02)01113-5Search in Google Scholar
Seeram, N. P. (2008). Berry fruits for cancer prevention: current status and future prospects. Journal of Agricultural and Food Chemistry, 56, 630–635. DOI: 10.1021/jf072504n.10.1021/jf072504n">10.1021/jf072504nSearch in Google Scholar
Shrivastava, A., & Gupta, V. B. (2011). Methods for the determination of limit of detection and limit of quantitation of the analytical methods. Chronicles of Young Scientists, 2, 21–25. DOI: 10.4103/2229-5186.79345.10.4103/2229-5186.79345">10.4103/2229-5186.79345Search in Google Scholar
Simić, A. Z., Verbić T. Ž., Sentić, M. N., Vojić, M.P., Juranić, I. O., & Manojlović, D. D. (2013). Study of ellagic acid electro-oxidation mechanism. Monatshefte für Chemie, 144, 121–128. DOI: 10.1007/s00706-012-0856-8.10.1007/s00706-012-0856-8">10.1007/s00706-012-0856-8Search in Google Scholar
Wada, L., & Ou, B. (2002). Antioxidant activity and phenolic content of Oregon caneberries. Journal of Agricultural and Food Chemistry, 50, 3495–3500. DOI: 10.1021/jf011405l.10.1021/jf011405l">10.1021/jf011405lSearch in Google Scholar
Wang, H., Cao, G., & Prior, R. L. (1996). Total antioxidant capacity of fruits. Journal of Agricultural and Food Chemistry, 44, 701–705. DOI: 10.1021/jf950579y.10.1021/jf950579y">10.1021/jf950579ySearch in Google Scholar
Wiczling, P., Markuszewski, M. J., & Kaliszan, R. (2004). Determination of pKa by pH gradient reversed-phase HPLC. Analytical Chemistry, 76, 3069–3077. DOI: 10.1021/ ac049807q.10.1021/ ac049807q">10.1021/ ac049807qSearch in Google Scholar
Williams, D. J., Edwards, D., Pun, S., Chaliha, M., & Sultanbawa, Y. (2014). Profiling ellagic acid content: The importance of form and ascorbic acid levels. Food Research International, 66, 100–106. DOI: 10.1016/j.foodres.2014.09.003.10.1016/j.foodres.2014.09.003">10.1016/j.foodres.2014.09.003Search in Google Scholar
Wolfbeis, O. S., & Hochmuth, P. (1986). The fluorescence of ellagic acid and its borax complex. Monatshefte für Chemie, 117, 369–374. DOI: 10.1007/bf00816531.10.1007/bf00816531">10.1007/bf00816531Search in Google Scholar
Zafrilla, P., Ferreres, F., & Tomas-Barberan, F. A. (2001). Effect of processing and storage on the antioxidant ellagic acid derivatives and flavonoids of red raspberry (Rubus idaeus) jams. Journal of Agricultural and Food Chemistry, 49, 3651– 3655. DOI: 10.1021/jf010192x10.1021/jf010192x">10.1021/jf010192xSearch in Google Scholar
© 2016 Institute of Chemistry, Slovak Academy of Sciences
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Articles in the same Issue
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- Bimetallic nickel and palladium complexes for catalytic applications
- Original Paper
- Enantiomeric purity control of R-cinacalcet in pharmaceutical product by capillary electrophoresis
- Original Paper
- Sensitive electrogravimetric immunoassay of hepatitis B surface antigen through hyperbranched polymer bridge linked to multiple secondary antibodies
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