journal article·2021-03-14Open access

Empirical Kinetic Modelling and Mechanisms of Quercetin Thermal Degradation in Aqueous Model Systems: Effect of pH and Addition of Antioxidants

Abdessamie Kellil, Spyros Grigorakis, Sofia Loupassaki, Dimitris P. Makris

Applied Sciences· Volume 11· Issue 6

Abstract

Quercetin (Qt) is a natural flavonoid of high biological significance, and it occurs in a wide variety of plant foods. Although its oxidation by various means has been extensively studied, its behavior with regard to thermal treatments remains a challenge. The study described herein aimed at investigating Qt thermal decomposition, by proposing an empirical sigmoidal model for tracing degradation kinetics. This model was employed to examine the effect of addition of antioxidants on Qt thermal degradation, including ascorbic acid, L-cysteine, and sulfite. Furthermore, degradation pathways were proposed by performing liquid chromatography-tandem mass spectrometry analyses. Upon addition of any antioxidant used, the sigmoidal course of Qt thermal degradation was pronounced, evidencing the validity of the empirical model used in the study of similar cases. The antioxidants retarded Qt degradation in a manner that appeared to depend on Qt/antioxidant molar ratio. No major differentiation in the degradation mechanism was observed in response to the addition of various antioxidants, and in all cases protocatechuic acid and phloroglucinol carboxylic acid were typical degradation products identified. Furthermore, in all cases tested the solutions resulted after thermal treatment possessed inferior antioxidant properties compared to the initial Qt solutions, and this demonstrated the detrimental effects of heating on Qt. The empirical model proposed could be of assistance in interpreting the degradation behavior of other polyphenols, but its validity merits further investigation.
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Research context

OpenAlex topics: Phytochemicals and Antioxidant Activities · Free Radicals and Antioxidants · Antioxidant Activity and Oxidative Stress

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Food Quality & Chemistry of Natural Products, Mediterranean Agronomic Institute of Chania (M.A.I.Ch.), International Centre for Advanced Mediterranean Agronomic Studies (CIHEAM), P.O. Box 85, 73100 Chania, Greece

Department of Food Science & Nutrition, School of Agricultural Sciences, University of Thessaly, N. Temponera Street, 43100 Karditsa, Greece

References (39)

Show source-provided references
1. The role of polyphenols in human health and food systems: A mini-review10.3389/fnut.2018.00087 ↗
2. Kamiloglu, S., Tomas, M., and Capanoglu, E. (2019). Dietary Flavonols and O-Glycosides. Handbook of Dietary Phytochemicals, Springer.10.1007/978-981-13-1745-3_4-1 ↗
3. Thermal degradation of flavonol glycosides in noni leaves during roasting
4. Calani, L., Dall’Asta, M., Bruni, R., and Rio, D.D. (2014). Flavonoid occurrence, bioavailability, metabolism, and protective effects in humans: Focus on Flavan-3-ols and Flavonols. Recent Advances in Polyphenol Research, John Wiley & Sons, Ltd.10.1002/9781118329634.ch8 ↗
5. The biological activities, chemical stability, metabolism and delivery systems of quercetin: A review10.1016/j.tifs.2016.07.004 ↗
6. Comparative analysis of quercetin oxidation by electrochemical, enzymatic, autoxidation, and free radical generation techniques: A mechanistic study10.1021/jf802413v ↗
7. Effect of thermal processing on the flavonols rutin and quercetin10.1002/rcm.2720 ↗
8. Quercetin and related flavonoids conserve their antioxidant properties despite undergoing chemical or enzymatic oxidation10.1016/j.foodchem.2017.05.023 ↗
9. Effect of heat processing on thermal stability and antioxidant activity of six flavonoids10.1111/jfpp.13203 ↗
10. Quercetin oxidation paradoxically enhances its antioxidant and cytoprotective properties10.1021/acs.jafc.7b05214 ↗
11. Effect of storage and domestic processing on the content and composition of flavonol glucosides in onion (Allium cepa)10.1021/jf9605916 ↗
12. Domestic processing of onion bulbs (Allium cepa) and asparagus spears (Asparagus officinalis): Effect on flavonol content and antioxidant status10.1021/jf001497z ↗
13. Human exposure modelling of quercetin in onions (Allium cepa L.) following thermal processing10.1016/j.foodchem.2015.04.035 ↗
14. Thermal degradation kinetics of bioactive compounds from black rice flour (Oryza sativa L.) extracts10.1016/j.jcs.2016.08.010 ↗
15. Thermal degradation of cloudy apple juice phenolic constituents10.1016/j.foodchem.2014.04.005 ↗
16. Quercetin in onion (Allium cepa L.) after heat-treatment simulating home preparation10.1016/j.jfca.2004.03.027 ↗
17. Influence of heat treatment on antioxidant capacity and (poly) phenolic compounds of selected vegetables10.1016/j.foodchem.2015.10.139 ↗
18. Kinetics and modeling of L-cysteine effect on the Cu (II)-induced oxidation of quercetin10.1080/00986445.2019.1574767 ↗
19. Correlation of pigment and flavanol content with antioxidant properties in selected aged regional wines from Greece10.1006/jfca.2002.1070 ↗
20. Interactions of quercetin with iron and copper ions: Complexation and autoxidation10.1080/10715760500484351 ↗
21. One-electron oxidation of quercetin and quercetin derivatives in protic and non protic media10.1039/a901460h ↗
22. Comparison of quercetin and a non-orthohydroxy flavonol as antioxidants by competing in vitro oxidation reactions10.1021/jf010107l ↗
23. Heat-induced, metal-catalyzed oxidative degradation of quercetin and rutin (quercetin 3-O-rhamnosylglucoside) in aqueous model systems10.1021/jf0001280 ↗
24. Kinetics and mechanism of quercetin oxidation10.1002/j.2050-0416.1972.tb03481.x ↗
25. Degradation kinetics of fisetin and quercetin in solutions as effected by pH, temperature and coexisted proteins10.2298/JSC150706092W ↗
26. Raman and surface-enhanced Raman scattering (SERS) investigation of the quercetin interaction with metals: Evidence of structural changing processes in aqueous solution and on metal nanoparticles10.1016/j.molstruc.2008.07.025 ↗
27. Effect of pH on the chemical modification of quercetin and structurally related flavonoids characterized by optical (UV-visible and Raman) spectroscopy10.1039/C4CP00864B ↗
28. Systematization of the results of the chromatography–mass spectrometry identification of the products of quercetin oxidation by atmospheric oxygen in aqueous solutions10.1134/S1061934817080147 ↗
29. Investigation on biocatalytic properties of a peroxidase-active homogenate from onion solid wastes: An insight into quercetin oxidation mechanism10.1016/j.procbio.2008.04.003 ↗
30. Hydroxyl free radical-mediated oxidative degradation of quercetin and morin: A preliminary investigation10.1006/jfca.2001.1030 ↗
31. Oxidative degradation of quercetin with hydrogen peroxide using continuous-flow kinetic electrospray–ion trap–time-of-flight mass spectrometry10.1021/jf500619x ↗
32. Antioxidant/prooxidant properties of model phenolic compounds: Part I. Studies on equimolar mixtures by chemiluminescence and cyclic voltammetry10.1016/j.foodchem.2010.08.076 ↗
33. Antioxidant/pro-oxidant properties of model phenolic compounds. Part II: Studies on mixtures of polyphenols at different molar ratios by chemiluminescence and LC–MS10.1016/j.foodchem.2012.01.057 ↗
34. Effect of natural antioxidants on heat-induced, copper (II)-catalysed, oxidative degradation of quercetin and rutin (quercetin 3-O-rutinoside) in aqueous model systems10.1002/jsfa.1159 ↗
35. Barberá, J.J., Metzger, A., and Wolf, M. (2000). Sulfites, thiosulfates, and dithionites. Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co.10.1002/14356007.a25_477 ↗
36. Electrochemical oxidation of wine polyphenols in the presence of sulfur dioxide10.1021/jf400282z ↗
37. Pharmacokinetic study of rutin and quercetin in rats after oral administration of total flavones of mulberry leaf extract10.1590/S0102-695X2013000500009 ↗
38. A novel method for identification and quantification of sulfated flavonoids in plants by neutral loss scan mass spectrometry10.3389/fpls.2019.00885 ↗
39. Amorati, R., Baschieri, A., Cowden, A., and Valgimigli, L. (2017). The antioxidant activity of quercetin in water solution. Biomimetics, 2.10.3390/biomimetics2030009 ↗