ORIGINAL ARTICLE
Thermal Decarboxylation of Betacyanins in Red Beet Betalain-Rich Extract
| 1 | Department of Analytical Chemistry, Institute C-1, Faculty of Chemical Engineering and Technology, Cracow University of Technology, ul. Warszawska 24, Cracow 31-155, Poland |
| 2 | Chemistry Research, VDF FutureCeuticals, Inc. Momence, IL 60954, USA; Food Science and Human Nutrition, University of Illinois at Urbana-Champaign, Urbana IL 61801, USA |
| 3 | ABC Clinical Research, FutureCeuticals, Inc., 23 Peter Canyon Rd, Irvine, CA 92606, USA |
CORRESPONDING AUTHOR
Submission date: 2019-09-17
Final revision date: 2019-11-22
Acceptance date: 2019-11-28
Online publication date: 2019-12-17
Publication date: 2020-02-12
Pol. J. Food Nutr. Sci. 2020;70(1):7–14
KEYWORDS
TOPICS
SpectrometryExtractionLiquid chromatographyNatural foodFunctional foodsCookingFood bioactivesVegetablesOrganic acidsPigments
ABSTRACT
Betalains are one of the most common groups of plant pigments found in nature, especially in red beetroot (Beta vulgaris L.) which is the main commercially exploited source of betalains produced in the form of concentrates or powders. This report presents results of thermal decarboxylation studies on betacyanins present in a specifically purified highly concentrated betalain-rich extract (BRE). The first tentative structures formed by decarboxylation of the main pigment present in BRE, betanin and its diastereomer, were established by means of liquid chromatography coupled to diode array detection and electrospray ionization tandem mass spectrometry (LC-DAD-ESI-MS/MS). In the extract, two new isomeric bidecarboxylated betanins were tentatively identified. A high rate of generation of 2-decarboxy-betanin/-isobetanin which are present in the BRE extract at very low level was observed, which was dependent on the starting concentration of the BRE substrate. The bidecarboxylated derivatives were generated at a higher rate mostly from 17-decarboxy-betanin/-isobetanin as well as 15-decarboxy-betanin by further decarboxylation at carbon C-2. Further studies will be performed to demonstrate if the decarboxylated betanins being products of heating B. vulgaris preparations can be used for various food applications with new health-promoting actions and colorant properties.
FUNDING
This research was financed by Polish National Science Centre project for the years 2018-2021 (Project No. UMO-2017/27/B/NZ9/02831).
REFERENCES (33)
1.
Altamirano, R.C., Drdak, M., Simon, P., Rajniakova, A., Karovicova, J., Preclik, L. (1993). Thermal degradation of betanine in various water alcohol model systems. Food Chemistry, 46(1), 73–75.
2.
Azeredo, H.M.C. (2009). Betalains: properties, sources, applications, and stability – a review. International Journal of Food Science & Technology, 44(12), 2365–2376.
3.
Cai, Y.Z., Sun, M., Xing, J., Luo, Q., Corke, H. (2006). Structure-radical scavenging activity relationships of phenolic compounds from traditional Chinese medicinal plants. Life Sciences, 78(25), 2872–2888.
4.
Cai, Y., Sun, M., Corke, H. (2003). Antioxidant activity of betalains from plants of the amaranthaceae. Journal of Agricultural and Food Chemistry, 51(8), 2288–2294.
5.
Cai, Y., Sun, M., Corke, H. (2005). Characterization and application of betalain pigments from plants of the Amaranthaceae. Trends in Food Science & Technology, 16(9), 370–376.
6.
Ciriminna, R., Fidalgo, A., Danzi, C., Timpanaro, G., Ilharco, I.M., Pagliaro, M. (2018). Betanin: A Bioeconomy insight into a valued betacyanin. ACS Sustainable Chemistry & Engineering, 6(3), 2860–2865.
7.
Chhikara, N., Kushwaha, K., Sharma, P., Gat, Y., Panghal, A. (2019). Bioactive compounds of beetroot and utilization in food processing industry: A critical review. Food Chemistry, 272, 192–200.
8.
Dunkelblum, E., Miller, H.E., Dreiding, A.S. (1972). On the mechanism of decarboxylation of betanidine. A contribution to the interpretation of the biosynthesis of betalaines. Helvetica Chimica Acta, 55(2), 642–648.
9.
Esatbeyoglu, T., Wagner, A.E., Schini-Kerth, V.B., Rimbach, G. (2015). Betanin - a food colorant with biological activity. Molecular Nutrition & Food Research, 59(1), SI, 36–47.
10.
Gandía-Herrero, F., Escribano, J., Garcia-Carmona, F. (2016). Biological activities of plant pigments betalains. Critical Reviews in Food Science and Nutrition, 56(6), 937–945.
11.
Gandía-Herrero, F., Escribano, J., Garcia-Carmona, F. (2009). The role of phenolic hydroxy groups in the free radical scavenging activity of betalains. Journal of Natural Products, 72(6), 1142–1146.
12.
Gengatharan, A., Dykes, G.A., Choo, W.S. (2015). Betalains: Natural plant pigments with potential application in functional foods. LWT - Food Science and Technology, 64(2), 645–649.
13.
Herbach, K.M., Stintzing, F.C., Carle, R. (2004). Impact of thermal treatment on color and pigment pattern of red beet (Beta vulgaris L.) preparations. Journal of Food Science, 69(6), C491-C498.
14.
Herbach, K.M., Stintzing, F.C., Carle, R. (2006). Betalain stability and degradation-structural and chromatic aspects. Journal of Food Science, 71(4), R41-R50.
15.
Herbach, K.M., Maier, C., Stintzing, F., Carle, R. (2007). Effects of processing and storage on juice colour and betacyanin stability of purple pitaya (Hylocereus polyrhizus) juice. European Food Research and Technology, 224(5), 649–658.
16.
Kapadia, G.J., Azuine, M.A., Sridhar, R., Okuda, Y., Tsuruta, A., Ichiishi, E., Mukainake, T., Takasaki, M., Konoshima, T., Nishino, H., Tokuda, H. (2003). Chemoprevention of DMBA-induced UV-B promoted, NOR-1-induced TPA promoted skin carcinogenesis, and DEN-induced phenobarbital promoted liver tumors in mice by extract of beetroot. Pharmacological Research, 47, 141–148.
17.
Kumorkiewicz, A., Wybraniec, S. (2017). Thermal degradation of major gomphrenin pigments in the fruit juice of Basella alba L. (Malabar Spinach). Journal of Agricultural and Food Chemistry, 65, 7500−7508.
18.
Martins, N., Roriz, C.L., Morales, P., Barros, L., Ferreira, I.C.F.R. (2017). Coloring attributes of betalains: a key emphasis on stability and future applications. Food & Function, 8(4), 1357–1372.
19.
Minale, L., Piattelli, S. (1965). Decarbossilazione termica dei betacianie delle betaxantine. Rendiconto dell’Accademia delle Scienze Fisiche e Matematiche, 32, 165.
20.
Nemzer, B., Pietrzkowski, Z., Spórna, A., Stalica, P., Thresher, W., Michałowski, T., Wybraniec, S. (2011). Betalainic and nutritional profiles of pigment-enriched red beet root (Beta vulgaris L.) dried extracts. Food Chemistry, 127, 42–53.
21.
Pietrzkowski, Z., Argumedo, R., Shu, C., Nemzer, B., Wybraniec, S., Reyes-Izquierdo, T. (2014). Betalain-rich red beet concentrate improves reduced knee discomfort and joint function: a double blind, placebo-controlled pilot clinical study. Nutrition and Dietary Supplements, 6, 9−13.
22.
Reddy, M.K., Alexander-Lindo, R.L., Nair, M.G. (2005). Relative inhibition of lipid peroxidation, cyclooxygenase enzymes, and human tumor cell proliferation by natural food colors. Journal of Agricultural and Food Chemistry, 53, 9268–9273.
23.
Siervo, M., Lara, J., Ogbonmwan, I., Mathers, J.C. (2013). Inorganic nitrate and beetroot juice supplementation reduces blood pressure in adults: a systematic review and meta-analysis. The Journal of Nutrition, 143, 818–826.
24.
Simon, P., Drda´k, M., Cruz Altamirano, R. (1993). Influence of water activity on the stability of betanin in various water/alcohol model systems. Food Chemistry, 46, 155-158.
25.
Stafford, H.A. (1994). Anthocyanins and betalains: evolution of the mutually exclusive pathways. Plant Science, 101, 91–98.
26.
Stintzing, F.C., Carle, R. (2004). Functional properties of anthocyanins and betalains in plants, food, and in human nutrition. Trends in Food Science & Technology, 15, 19–38.
27.
Tang, C.B., Zhang, W.G., Dai, C., Li, H.X., Xu, X.L., Zhou, G.H. (2015). Identification and quantification of adducts between oxidized rosmarinic acid and thiol compounds by UHPLC-LTQ-Orbitrap and MALDI-TOF/TOF tandem mass spectrometry. Journal of Agricultural and Food Chemistry, 63, 902−911.
28.
Tesoriere, L., Butera, D., Allegra, M., Fazzari, M., Livrea, M. (2005). Distribution of betalain pigments in red blood cells after consumption of cactus pear fruits and increased resistance of the cells to ex vivo induced oxidative hemolysis in humans. Journal of Agricultural and Food Chemistry, 53, 1266–1270.
29.
Wu, L.C., Hsu, H.W., Chen, Y.C., Chiu, C.C., Lin, Y.I., Ho, J.A. (2006). Antioxidant and antiproliferative activities of red pitaya. Food Chemistry, 95, 319–327.
30.
Vulić, J.J., Cebović, T.N., Canadanović, V.M., Cetković, G.S., Djilas, S.M., Canadanović-Brunet, J.M., Velićanski, A.S., Cvetković, D.D., Tumbas, V.T. (2013). Antiradical, antimicrobial and cytotoxic activities of commercial beetroot pomace. Food & Function, 4, 713–721.
31.
Wybraniec, S. (2005). Formation of decarboxylated betacyanins in heated purified betacyanin fractions from red beet root (Beta vulgaris L.) monitored by LC-MS/MS. Journal of Agricultural and Food Chemistry, 53(9), 3483–3487.
32.
Wybraniec, S., Mizrahi, Y. (2005). Generation of decarboxylated and dehydrogenated betacyanins in thermally treated purified fruit extract from purple pitaya (Hylocereus polyrhizus) monitored by LC-MS/MS. Journal of Agricultural and Food Chemistry, 53(17), 6704–6712.
33.
Wybraniec, S., Nowak-Wydra, B., Mizrahi, Y. (2006). 1H and 13C NMR spectroscopic structural elucidation of new decarboxylated betacyanins. Tetrahedron Letters, 47(11), 1725-1728.
CITATIONS (2):
1.
Thematic Issue on “Red Beetroot as a Source of Nutrients, Bioactive Compounds and Pigments”
Wiesław Wiczkowski
Polish Journal of Food and Nutrition Sciences
Wiesław Wiczkowski
Polish Journal of Food and Nutrition Sciences
2.
Phytochemical Molecules from the Decarboxylation of Gomphrenins in Violet Gomphrena globosa L.—Floral Infusions from Functional Food
Natalia Drobnicka, Katarzyna Sutor, Agnieszka Kumorkiewicz-Jamro, Aneta Spórna-Kucab, Michał Antonik, Ewa Dziedzic, Tomasz Świergosz, Joanna Ortyl, Sławomir Wybraniec
International Journal of Molecular Sciences
Natalia Drobnicka, Katarzyna Sutor, Agnieszka Kumorkiewicz-Jamro, Aneta Spórna-Kucab, Michał Antonik, Ewa Dziedzic, Tomasz Świergosz, Joanna Ortyl, Sławomir Wybraniec
International Journal of Molecular Sciences
