Abstract
The antioxidant capacity of 22 kinds of fruits was measured by the developed electron spin resonance (ESR) method based on Cu2+ sensor. Cu2+ is reduced to Cu+ by the antioxidants in the fruits, and the remaining Cu2+ was determined by ESR and UV-Vis spectroscopy. Cu2+ can give an ESR signal whereas Cu+ cannot, and the loss of the ESR signal was used to quantify the antioxidant capacity of various fruits. The results were shown as vitamin C equivalent antioxidant capacity (VCEAC). The VCEAC values obtained by ESR and UV-Vis methods ranged from 24.23 to 688.61 mg/100 g and from 24.12 to 677.79 mg/100 g, respectively. Cupric ion reducing antioxidant capacity (CUPRAC) and 1,1-diphenyl-2-picryl-hydrazyl (DPPH) methods were employed for comparison. Based on Pearson’s correlation test, the results obtained by CUPRAC and DPPH methods were both significantly correlated with these obtained by the present method, which indicated that the novel method was reliable. Total phenolic content for all kinds of fruits was measured with the Folin–Ciocalteu reagent, and VCEAC values obtained by the ESR method were significantly correlated with total phenolic contents.
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References
Young IS, Woodside JV. Antioxidants in health and disease. J Clin Pathol. 2001;54:176–86.
Droge W. Free radicals in the physiological control of cell function. Physiol Rev. 2002;82:47–95.
Jiang LY, He S, Pan YJ, Sun CR. Bioassay-guided isolation and EPR-assisted antioxidant evaluation of two valuable compounds from mango peels. Food Chem. 2010;119:1285–92.
Stocker P, Lesgards JF, Vidal N, Chalier F, Prost M. ESR study of a biological assay on whole blood: antioxidant efficiency of various vitamins. Biochim Biophys Acta Gen Subj. 2003;1621:1–8.
Poprac P, Jomova K, Simunkova M, Kollar V, Rhodes CJ, Valko M. Targeting free radicals in oxidative stress-related human diseases. Trends Pharmacol Sci. 2017;38:592–607.
Chan C-L, Gan R-Y, Corke H. The phenolic composition and antioxidant capacity of soluble and bound extracts in selected dietary spices and medicinal herbs. Int J Food Sci Tech. 2016;51:565–73.
Živković J, Zeković Z, Mujić I, Gođevac D, Mojović M, Mujić A, et al. EPR spin-trapping and spin-probing spectroscopy in assessing antioxidant properties: example on extracts of catkin, leaves, and spiny burs of castanea sativa. Food Biophys. 2009;4:126–33.
Li Y, Bao T, Chen W. Comparison of the protective effect of black and white mulberry against ethyl carbamate-induced cytotoxicity and oxidative damage. Food Chem. 2018;243:65–73.
Contreras-Calderón J, Calderón-Jaimes L, Guerra-Hernández E, García-Villanova B. Antioxidant capacity, phenolic content and vitamin C in pulp, peel and seed from 24 exotic fruits from Colombia. Food Res Int. 2011;44:2047–53.
Jiao Y, Kilmartin PA, Fan M, Quek SY. Assessment of phenolic contributors to antioxidant activity of new kiwifruit cultivars using cyclic voltammetry combined with HPLC. Food Chem. 2018;268:77–85.
Jez M, Wiczkowski W, Zielinska D, Bialobrzewski I, Blaszczak W. The impact of high pressure processing on the phenolic profile, hydrophilic antioxidant and reducing capacity of puree obtained from commercial tomato varieties. Food Chem. 2018;261:201–9.
Diaconeasa Z, Leopold L, Rugina D, Ayvaz H, Socaciu C. Antiproliferative and antioxidant properties of anthocyanin rich extracts from blueberry and blackcurrant juice. Int J Food Sci Tech. 2015;16:2352–65.
Wang H, Guo X, Hu X, Li T, Fu X, Liu RH. Comparison of phytochemical profiles, antioxidant and cellular antioxidant activities of different varieties of blueberry (Vaccinium spp.). Food Chem. 2017;217:773–81.
Shahidi F, Zhong Y. Measurement of antioxidant activity. J Funct Foods. 2015;18:757–81.
Assefa AD, Keum Y-S, Saini RK. A comprehensive study of polyphenols contents and antioxidant potential of 39 widely used spices and food condiments. J Food Meas Charact. 2018;12:1548–55.
Ambigaipalan P, de Camargo AC, Shahidi F. Identification of phenolic antioxidants and bioactives of pomegranate seeds following juice extraction using HPLC-DAD-ESI-MS(n). Food Chem. 2017;221:1883–94.
Sentkowska A, Pyrzynska K. Investigation of antioxidant interaction between green tea polyphenols and acetaminophen using isobolographic analysis. J Pharm Biomed Anal. 2018;159:393–7.
Thaipong K, Boonprakob U, Crosby K, Cisneros-Zevallos L, Hawkins BD. Comparison of ABTS, DPPH, FRAP, and ORAC assays for estimating antioxidant activity from guava fruit extracts. J Food Compos Anal. 2006;19:669–75.
Vignault A, Gonzalez-Centeno MR, Pascual O, Gombau J, Jourdes M, Moine V, et al. Chemical characterization, antioxidant properties and oxygen consumption rate of 36 commercial oenological tannins in a model wine solution. Food Chem. 2018;268:210–9.
Ioannone F, Di Mattia CD, De Gregorio M, Sergi M, Serafini M, Sacchetti G. Flavanols, proanthocyanidins and antioxidant activity changes during cocoa (Theobroma cacao L.) roasting as affected by temperature and time of processing. Food Chem. 2015;174:256–62.
Floegel A, Kim D-O, Chung S-J, Koo SI, Chun OK. Comparison of ABTS/DPPH assays to measure antioxidant capacity in popular antioxidant-rich US foods. J Food Compos Anal. 2011;24:1043–8.
Elias RJ, Andersen ML, Skibsted LH, Waterhouse AL. Identification of free radical intermediates in oxidized wine using electron paramagnetic resonance spin trapping. J Agric Food Chem. 2009;57:4359–65.
Bartoš J, Švajdlenková H, Zaleski R, Edelmann M, Lukešová M. Spin probe dynamics in relation to free volume in crystalline organics by means of ESR and PALS: n-hexadecane. Phys B Condens Matter. 2013;430:99–105.
Weil J. A review of electron spin spectroscopy and its application to the study of paramagnetic defects in crystalline quartz. Phys Chem Miner. 1984;10:149–65.
Minakata K, Suzuki O. Quantitation of manganese by use of an electron spin resonance method. Anal Chem. 2002;74:6111–3.
Morsy MA, Sultan SM, Dafalla H. Electron paramagnetic resonance method for the quantitative assay of ketoconazole in pharmaceutical preparations. Anal Chem. 2009;81:6991–5.
Borbat PP, Costa-Filho AJ, Earle KA, Moscicki JK, Freed JH. Electron spin resonance in studies of membranes and proteins. Science. 2001;291:266–9.
Webb MI, Walsby CJ. EPR as a probe of the intracellular speciation of ruthenium(III) anticancer compounds. Metallomics. 2013;5:1624–33.
Polovka M. EPR spectroscopy a tool to characterize stability. J Food Nutr Res. 2006;45:1–11.
Escudero R, Segura J, Velasco R, Valhondo M, Romero de Avila MD, Garcia-Garcia AB, et al. Electron spin resonance (ESR) spectroscopy study of cheese treated with accelerated electrons. Food Chem. 2019;276:315–21.
Tian S, Jiang J, Zang S, Wang K, Yu Y, Li X, et al. Determination of IgG by electron spin resonance spectroscopy using Fe3O4 nanoparticles as probe. Microchem J. 2018;141:444–50.
Jiang J, Tian S, Wang K, Wang Y, Zang S, Yu A, et al. Electron spin resonance spectroscopy for immunoassay using iron oxide nanoparticles as probe. Anal Bioanal Chem. 2018;410:1817–24.
Bartoszek M, Polak J. A comparison of antioxidative capacities of fruit juices, drinks and nectars, as determined by EPR and UV-vis spectroscopies. Spectrochim Acta A Mol Biomol. 2016;153:546–9.
Zang S, Tian S, Jiang J, Han D, Yu X, Wang K, et al. Determination of antioxidant capacity of diverse fruits by electron spin resonance (ESR) and UV-vis spectrometries. Food Chem. 2017;221:1221–5.
Azman NA, Peiro S, Fajari L, Julia L, Almajano MP. Radical scavenging of white tea and its flavonoid constituents by electron paramagnetic resonance (EPR) spectroscopy. J Agric Food Chem. 2014;62:5743–8.
Polak J, Bartoszek M, Stanimirova I. A study of the antioxidant properties of beers using electron paramagnetic resonance. Food Chem. 2013;141:3042–9.
Li D, Jiang J, Han D, Yu X, Wang K, Zang S, et al. Measurement of antioxidant capacity by electron spin resonance spectroscopy based on copper(II) reduction. Anal Chem. 2016;88:3885–90.
Jiang J, Zang S, Li D, Wang K, Tian S, Yu A, et al. Determination of antioxidant capacity of thiol-containing compounds by electron spin resonance spectroscopy based on Cu2+ ion reduction. Talanta. 2018;184:23–8.
Apak R, Güçlü K, Özyürek M, Çelik SE. Mechanism of antioxidant capacity assays and the CUPRAC (cupric ion reducing antioxidant capacity) assay. Microchim Acta. 2007;160:413–9.
Sellappan S, Akoh C, Krewer G. Phenolic compounds and antioxidant capacity of Georgia-grown blueberries and blackberries. J Agric Food Chem. 2002;50:2432–8.
Özyürek M, Güçlü K, Apak R. The main and modified CUPRAC methods of antioxidant measurement. Trends Analyt Chem. 2011;30:652–64.
Piljac-Žegarac J, Valek L, Martinez S, Belščak A. Fluctuations in the phenolic content and antioxidant capacity of dark fruit juices in refrigerated storage. Food Chem. 2009;113:394–400.
Locatelli M, Gindro R, Travaglia F, Coïsson J-D, Rinaldi M, Arlorio M. Study of the DPPH-scavenging activity: development of a free software for the correct interpretation of data. Food Chem. 2009;114:889–97.
Velioglu YS, Mazza G, Gao L, Oomah BD. Antioxidant activity and total phenolics in selected fruits, vegetables, and grain products. J Agric Food Chem. 1998;46:4113–7.
Vasco C, Ruales J, Kamal-Eldin A. Total phenolic compounds and antioxidant capacities of major fruits from Ecuador. Food Chem. 2008;111:816–23.
Fu L, Xu BT, Xu XR, Gan RY, Zhang Y, Xia EQ, et al. Antioxidant capacities and total phenolic contents of 62 fruits. Food Chem. 2011;129:345–50.
Funding
This work was supported by the Science and Technology Development Planning Project of Jilin Province (Grant No. 20180201027GX and 20180201059SF) and the National Natural Science Foundation of China (Grant No. 31300621).
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Tian, S., Li, X., Jiang, J. et al. Application of Cu2+-based electron spin resonance spectroscopy in measurement of antioxidant capacity of fruits. Anal Bioanal Chem 411, 6677–6686 (2019). https://doi.org/10.1007/s00216-019-02041-4
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DOI: https://doi.org/10.1007/s00216-019-02041-4