Açaí (Euterpe oleracea Mart.) Seed Extracts from Different Varieties: A Source of Proanthocyanidins and Eco-Friendly Corrosion Inhibition Activity
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. Materials
3.2. Extraction Procedures
3.3. Ethyl Acetate:Water Liquid–Liquid Partitioning
3.4. Proanthocyanidin Content by n-BuOH/HCl Test
3.5. HILIC–HPLC–FLD Proanthocyanidin Analysis
3.6. MALDI-TOF-MS
3.7. Direct Infusion ESI-MS/MS Analysis
3.8. Phloroglucinolysis
3.9. HPLC–DAD–ESI-TOF-MS
3.10. Corrosion Experiments
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
- Smith, N. Palms and People in the Amazon; Geobotany Studies; Springer International Publishing: Cham, Switzerland, 2015; ISBN 978-3-319-05508-4. [Google Scholar]
- Heinrich, M.; Dhanji, T.; Casselman, I. Açaí (Euterpe oleracea Mart.)—A phytochemical and pharmacological assessment of the species’ health claims. Phytochem. Lett. 2011, 4, 10–21. [Google Scholar] [CrossRef] [Green Version]
- Wycoff, W.; Luo, R.; Schauss, A.G.; Neal-Kababick, J.; Sabaa-Srur, A.U.O.; Maia, J.G.S.; Tran, K.; Richards, K.M.; Smith, R.E. Chemical and nutritional analysis of seeds from purple and white açaí (Euterpe oleracea Mart.). J. Food Compos. Anal. 2015, 41, 181–187. [Google Scholar] [CrossRef]
- Schauss, A.G. Advances in the study of the health benefits and mechanisms of action of the pulp and seed of the Amazonian palm fruit, Euterpe oleracea Mart., known as “Açai”. In Fruits, Vegetables, and Herbs; Elsevier Inc.: Oxford, UK, 2016; ISBN 9780128029893. [Google Scholar]
- da Silveira, T.F.F.; de Souza, T.C.L.; Carvalho, A.V.; Ribeiro, A.B.; Kuhnle, G.G.C.; Godoy, H.T. White açaí juice (Euterpe oleracea): Phenolic composition by LC-ESI-MS/MS, antioxidant capacity and inhibition effect on the formation of colorectal cancer related compounds. J. Funct. Foods 2017, 36, 215–223. [Google Scholar] [CrossRef]
- Rufino, M.d.S.M.; Pérez-Jiménez, J.; Arranz, S.; Alves, R.E.; de Brito, E.S.; Oliveira, M.S.P.; Saura-Calixto, F. Açaí (Euterpe oleraceae) “BRS Pará”: A tropical fruit source of antioxidant dietary fiber and high antioxidant capacity oil. Food Res. Int. 2011, 44, 2100–2106. [Google Scholar] [CrossRef] [Green Version]
- Melo, P.S.; Selani, M.M.; Gonçalves, R.H.; de Oliveira Paulino, J.; Massarioli, A.P.; de Alencar, S.M. Açaí seeds: An unexplored agro-industrial residue as a potential source of lipids, fibers, and antioxidant phenolic compounds. Ind. Crops Prod. 2021, 161, 113204. [Google Scholar] [CrossRef]
- Pessoa, J.D.C.; Arduin, M.; Martins, M.A.; de Carvalho, J.E.U. Characterization of açaí (E. oleracea) fruits and its processing residues. Braz. Arch. Biol. Technol. 2010, 53, 1451–1460. [Google Scholar] [CrossRef] [Green Version]
- Monteiro, A.F.; Miguez, I.S.; Silva, J.P.R.B.; da Silva, A.S. High concentration and yield production of mannose from açaí (Euterpe oleracea Mart.) seeds via mannanase-catalyzed hydrolysis. Sci. Rep. 2019, 9, 10939. [Google Scholar] [CrossRef] [Green Version]
- Melo, P.S.; de Oliveira Rodrigues Arrivetti, L.; de Alencar, S.M.; Skibsted, L.H. Antioxidative and prooxidative effects in food lipids and synergism with α-tocopherol of açaí seed extracts and grape rachis extracts. Food Chem. 2016, 213, 440–449. [Google Scholar] [CrossRef]
- Martins, G.R.; do Amaral, F.R.L.; Brum, F.L.; Mohana-Borges, R.; de Moura, S.S.T.; Ferreira, F.A.; Sangenito, L.S.; Santos, A.L.S.; Figueiredo, N.G.; da Silva, A.S. Chemical characterization, antioxidant and antimicrobial activities of açaí seed (Euterpe oleracea Mart.) extracts containing A- and B-type procyanidins. LWT 2020, 132, 109830. [Google Scholar] [CrossRef]
- Barros, L.; Calhelha, R.C.; Queiroz, M.J.R.P.; Santos-Buelga, C.; Santos, E.A.; Regis, W.C.B.; Ferreira, I.C.F.R. The powerful in vitro bioactivity of Euterpe oleracea Mart. seeds and related phenolic compounds. Ind. Crops Prod. 2015, 76, 318–322. [Google Scholar] [CrossRef] [Green Version]
- De Moura, R.S.; Pires, K.M.P.; Ferreira, T.S.; Lopes, A.A.; Nesi, R.T.; Resende, A.C.; Sousa, P.J.C.; da Silva, A.J.R.; Porto, L.C.; Valenca, S.S. Addition of açaí (Euterpe oleracea) to cigarettes has a protective effect against emphysema in mice. Food Chem. Toxicol. 2011, 49, 855–863. [Google Scholar] [CrossRef] [PubMed]
- De Oliveira, P.R.B.; Da Costa, C.A.; De Bem, G.F.; Cordeiro, V.S.C.; Santos, I.B.; De Carvalho, L.C.R.M.; Da Conceição, E.P.S.; Lisboa, P.C.; Ognibene, D.T.; Sousa, P.J.C.; et al. Euterpe oleracea Mart.-derived polyphenols protect mice from diet-induced obesity and fatty liver by regulating hepatic lipogenesis and cholesterol excretion. PLoS ONE 2015, 10, e0143721. [Google Scholar] [CrossRef] [Green Version]
- Zapata-Sudo, G.; da Silva, J.S.; Pereira, S.L.; Souza, P.J.; de Moura, R.S.; Sudo, R.T. Oral treatment with Euterpe oleracea Mart. (açaí) extract improves cardiac dysfunction and exercise intolerance in rats subjected to myocardial infarction. BMC Complement. Altern. Med. 2014, 14, 227. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Hümmer, W.; Schreier, P. Analysis of proanthocyanidins. Mol. Nutr. Food Res. 2008, 52, 1381–1398. [Google Scholar] [CrossRef]
- Ou, K.; Gu, L. Absorption and metabolism of proanthocyanidins. J. Funct. Foods 2014, 7, 43–53. [Google Scholar] [CrossRef]
- Ping, L.; Brosse, N.; Chrusciel, L.; Navarrete, P.; Pizzi, A. Extraction of condensed tannins from grape pomace for use as wood adhesives. Ind. Crops Prod. 2011, 33, 253–257. [Google Scholar] [CrossRef]
- Filgueira, D.; Moldes, D.; Fuentealba, C.; García, D.E. Condensed tannins from pine bark: A novel wood surface modifier assisted by laccase. Ind. Crops Prod. 2017, 103, 185–194. [Google Scholar] [CrossRef]
- Shirmohammadli, Y.; Efhamisisi, D.; Pizzi, A. Tannins as a sustainable raw material for green chemistry: A review. Ind. Crops Prod. 2018, 126, 316–332. [Google Scholar] [CrossRef]
- Neto, R.T.; Santos, S.A.O.; Oliveira, J.; Silvestre, A.J.D. Biorefinery of high polymerization degree proanthocyanidins in the context of circular economy. Ind. Crops Prod. 2020, 151, 112450. [Google Scholar] [CrossRef]
- Koch, G.; Varney, J.; Thopson, N.; Moghissi, O.; Gould, M.; Payer, J. International Measures of Prevention, Application, and Economics of Corrosion Technologies Study. NACE Int. 2016, 1–216. [Google Scholar]
- Miralrio, A.; Vázquez, A.E. Plant extracts as green corrosion inhibitors for different metal surfaces and corrosive media: A review. Processes 2020, 8, 942. [Google Scholar] [CrossRef]
- Tan, K.W.; Kassim, M.J.; Oo, C.W. Possible improvement of catechin as corrosion inhibitor in acidic medium. Corros. Sci. 2012, 65, 152–162. [Google Scholar] [CrossRef]
- Agi, A.; Junin, R.; Rasol, M.; Gbadamosi, A.; Gunaji, R. Treated Rhizophora mucronata tannin as a corrosion inhibitor in chloride solution. PLoS ONE 2018, 13, e0200595. [Google Scholar] [CrossRef]
- Tan, K.W.; Kassim, M.J. A correlation study on the phenolic profiles and corrosion inhibition properties of mangrove tannins (Rhizophora apiculata) as affected by extraction solvents. Corros. Sci. 2011, 53, 569–574. [Google Scholar] [CrossRef]
- Guedes, D.; Martins, G.R.; Jaramillo, L.Y.A.; Simas Bernardes Dias, D.; da Silva, A.J.R.; Lutterbach, M.T.S.; Reznik, L.Y.; Sérvulo, E.F.C.; Alviano, C.S.; Alviano, D.S. Proanthocyanidins with Corrosion Inhibition Activity for AISI 1020 Carbon Steel under Neutral pH Conditions of Coconut (Cocos nucifera L.) Husk Fibers. ACS Omega 2021, 6, 6893–6901. [Google Scholar] [CrossRef]
- Calicioglu, Ö.; Bogdanski, A. Linking the bioeconomy to the 2030 sustainable development agenda: Can SDG indicators be used to monitor progress towards a sustainable bioeconomy? New Biotechnol. 2021, 61, 40–49. [Google Scholar] [CrossRef]
- Romão, M.H.; de Bem, G.F.; Santos, I.B.; de Andrade Soares, R.; Ognibene, D.T.; de Moura, R.S.; da Costa, C.A.; Resende, Â.C. Açaí (Euterpe oleracea Mart.) seed extract protects against hepatic steatosis and fibrosis in high-fat diet-fed mice: Role of local renin-angiotensin system, oxidative stress and inflammation. J. Funct. Foods 2020, 65, 103726. [Google Scholar] [CrossRef]
- de Souza da Silva, A.; Nunes, D.V.Q.; de Carvalho, L.C.d.R.M.; Santos, I.B.; de Menezes, M.P.; de Bem, G.F.; da Costa, C.A.; de Moura, R.S.; Resende, A.C.; Ognibene, D.T. Açaí (Euterpe oleracea Mart) seed extract protects against maternal vascular dysfunction, hypertension, and fetal growth restriction in experimental preeclampsia. Hypertens. Pregnancy 2020, 39, 211–219. [Google Scholar] [CrossRef]
- Monteiro, E.B.; Soares, E.D.R.; Trindade, P.L.; Bem, G.F.; Resende, A.C.; Passos, M.M.C.D.F.; Soulage, C.O.; Daleprane, J.B. Uraemic toxin-induced inflammation and oxidative stress in human endothelial cells: Protective effect of polyphenol-rich extract from açaí. Exp. Physiol. 2020, 105, 542–551. [Google Scholar] [CrossRef] [PubMed]
- Makkar, H.P.S. Quantification of Tannins in Tree and Shrub Foliage; Springer: Dordrecht, The Netherlands, 2003; ISBN 978-90-481-6428-8. [Google Scholar]
- Kelm, M.A.; Johnson, J.C.; Robbins, R.J.; Hammerstone, J.F.; Schmitz, H.H. High-performance liquid chromatography separation and purification of cacao (Theobroma cacao L.) procyanidins according to degree of polymerization using a diol stationary phase. J. Agric. Food Chem. 2006, 54, 1571–1576. [Google Scholar] [CrossRef] [PubMed]
- Robbins, R.J.; Leonczak, J.; Johnson, J.C.; Li, J.; Kwik-Uribe, C.; Prior, R.L.; Gu, L. Method performance and multi-laboratory assessment of a normal phase high pressure liquid chromatography-fluorescence detection method for the quantitation of flavanols and procyanidins in cocoa and chocolate containing samples. J. Chromatogr. A 2009, 1216, 4831–4840. [Google Scholar] [CrossRef]
- Lin, L.-Z.; Sun, J.; Chen, P.; Monagas, M.J.; Harnly, J.M. UHPLC-PDA-ESI/HRMS n Profiling Method To Identify and Quantify Oligomeric Proanthocyanidins in Plant Products. J. Agric. Food Chem. 2014, 62, 9387–9400. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Soares, E.R.; Monteiro, E.B.; de Bem, G.F.; Inada, K.O.P.; Torres, A.G.; Perrone, D.; Soulage, C.O.; Monteiro, M.C.; Resende, A.C.; Moura-Nunes, N.; et al. Up-regulation of Nrf2-antioxidant signaling by Açaí (Euterpe oleracea Mart.) extract prevents oxidative stress in human endothelial cells. J. Funct. Foods 2017, 37, 107–115. [Google Scholar] [CrossRef]
- Monagas, M.; Quintanilla-López, J.E.; Gómez-Cordovés, C.; Bartolomé, B.; Lebrón-Aguilar, R. MALDI-TOF MS analysis of plant proanthocyanidins. J. Pharm. Biomed. Anal. 2010, 51, 358–372. [Google Scholar] [CrossRef]
- Pal, A.; Das, C. A novel use of solid waste extract from tea factory as corrosion inhibitor in acidic media on boiler quality steel. Ind. Crops Prod. 2020, 151, 112468. [Google Scholar] [CrossRef]
- Sastri, V.S. Green Corrosion Inhibitors; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2011; ISBN 9781118015438. [Google Scholar]
- Popov, B.N. Corrosion Engineering; Elsevier: Amsterdam, The Netherlands, 2015; ISBN 9780444627223. [Google Scholar]
- Zmozinski, A.V.; Peres, R.S.; Freiberger, K.; Ferreira, C.A.; Tamborim, S.M.M.; Azambuja, D.S. Zinc tannate and magnesium tannate as anticorrosion pigments in epoxy paint formulations. Prog. Org. Coat. 2018, 121, 23–29. [Google Scholar] [CrossRef]
- Merchan-Arenas, D.; Sanabria-Cala, J.; Cortes-Castillo, L.; Camacho, D.; Vesga, G.; Peña-Ballesteros, D.; Kouznetsov, V. Electrochemical evaluation of the corrosion rate inhibition capacity of eugenol, o-eugenol and diphenol, on AISI 1020 Steel Exposed to 1M HCl Medium. Chem. Eng. Trans. 2018, 64, 247–252. [Google Scholar] [CrossRef]
- Saxena, A.; Prasad, D.; Haldhar, R.; Singh, G.; Kumar, A. Use of Saraca ashoka extract as green corrosion inhibitor for mild steel in 0.5 M H2SO4. J. Mol. Liq. 2018, 258, 89–97. [Google Scholar] [CrossRef]
- Nardeli, J.V.; Fugivara, C.S.; Taryba, M.; Pinto, E.R.P.; Montemor, M.F.; Benedetti, A.V. Tannin: A natural corrosion inhibitor for aluminum alloys. Prog. Org. Coat. 2019, 135, 368–381. [Google Scholar] [CrossRef]
- Kennedy, J.A. Proanthocyanidins: Extraction, Purification, and Determination of Subunit Composition by HPLC. Curr. Protoc. Food Anal. Chem. 2002, 6, I1.4.1–I1.4.11. [Google Scholar] [CrossRef]
- Karonen, M.; Liimatainen, J.; Sinkkonen, J. Birch inner bark procyanidins can be resolved with enhanced sensitivity by hydrophilic interaction HPLC-MS. J. Sep. Sci. 2011, 34, 3158–3165. [Google Scholar] [CrossRef] [PubMed]
Results/Samples | PA | WA | BRS | |
---|---|---|---|---|
Extraction yield (%) | 8.04 (±0.85) | 7.61 (±0.78) | 6.99 (±1.25) | |
Liquid–Liquid Partitioning | EtOAc fraction yield (%) | 9.6 | 15.6 | 8.7 |
Aqueous fraction yield (%) | 87.4 | 83.1 | 75.9 | |
PAC content (%/dry matter) | 22.4 ± 5.0 | 6.4 ± 0.6 | 11.5 ± 3.8 | |
mDP by acid catalysis | 10.29 ± 0.01 [0.07] | 11.23 ± 0.09 [0.84] | 11.81 ± 0.09 [0.74] | |
Terminal subunit composition in (%) of (+)-catechin | 86.22 ± 0.19 [0.22] | 83.28 ± 0.34 [0.41] | 84.91 ± 0.51 [0.61] | |
Conversion yield (%) | 98.7 | 84.3 | 121.5 |
PA | WA | BRS | ||||
---|---|---|---|---|---|---|
Molecular ion [M − H]− (m/z) | MS2 (m/z) | Molecular ion [M − H]− (m/z) | MS2 (m/z) | Molecular ion [M − H]− (m/z) | MS2 (m/z) | Identification |
289.1 | 245; 205 | 289.1 | 245; 205 | 289.1 | 245; 205 | (epi)catechin |
577.2 | 425; 407; 289; 451; 287 | 577.2 | 407; 425; 289; 451; 287 | 577.2 | 451; 425; 407; 289; 287 | B-type procyanidin dimer |
421.28 | 289 | 421.2 | 289 | 421.25 | 289 | (epi)catechin-pentoside |
- | - | 469.1 | 289 | - | Unknown compound |
PA | WA | BRS | |||||
---|---|---|---|---|---|---|---|
DP | Predicted [M + Na]+ (Da) | Observed [M + Na]+ (Da) | Observed [M + Na]+ (Da) | Observed [M + Na]+ (Da) | Monomeric Units | ||
(epi)catechin | (epi)gallocatechin | Galloyl | |||||
3 | 889.8 | 889.7 | 889.9 | 889.6 | 3 | 0 | 0 |
905.8 | 904.8 | 905.8 | 905.5 | 2 | 1 | 0 | |
4 | 1178.0 | 1177.8 | 1178.2 | 1177.9 | 4 | 0 | 0 |
1194.0 | 1193.3 | 1194.2 | 1193.8 | 3 | 1 | 0 | |
1330.1 | 1329.4 | - | 1330.0 | 4 | 0 | 1 | |
5 | 1466.3 | 1466.1 | 1466.6 | 1466.2 | 5 | 0 | 0 |
1482.3 | 1481.5 | 1482.8 | 1482.0 | 4 | 1 | 0 | |
1618.4 | 1618.6 | - | 1618.3 | 5 | 0 | 1 | |
6 | 1754.5 | 1754.5 | 1755.7 | 1754.4 | 6 | 0 | 0 |
1770.5 | 1770.0 | 1771.3 | 1770.1 | 5 | 1 | 0 | |
1906.6 | 1906.5 | - | 1906.4 | 6 | 0 | 1 | |
7 | 2042.8 | 2042.6 | 2043.9 | 2042.7 | 7 | 0 | 0 |
2058.8 | 2058.0 | 2060.1 | 2058.6 | 6 | 1 | 0 | |
2194.9 | 2193.4 | - | 2194.4 | 7 | 0 | 1 | |
8 | 2331.0 | 2330.8 | 2332.6 | 2330.9 | 8 | 0 | 0 |
2347.0 | 2346.0 | 2347.8 | 2346.3 | 7 | 1 | 0 | |
2483.1 | 2483.5 | - | 2483.5 | 8 | 0 | 1 | |
9 | 2619.3 | 2619.0 | 2621.3 | 2619.1 | 9 | 0 | 0 |
2635.3 | 2634.3 | 2636.4 | 2634.4 | 8 | 1 | 0 | |
2771.4 | 2771.0 | - | 2770.9 | 9 | 0 | 1 | |
10 | 2907.6 | 2907.0 | 2907.5 | 2907.1 | 10 | 0 | 0 |
2923.5 | 2921.9 | 2924.6 | 2922.6 | 9 | 1 | 0 | |
3059.6 | 3058.1 | - | 3059.7 | 10 | 0 | 1 | |
11 | 3195.8 | 3195.4 | 3196.2 | 3195.1 | 11 | 0 | 0 |
3211.8 | 3211.0 | - | 3210.6 | 10 | 1 | 0 |
Concentration (g/L) | Tafel Data | LPR Data | Corrosion Rate (mm/year) | |||||
---|---|---|---|---|---|---|---|---|
Ecorr (mV, SCE) | βanodic (mVdec−1) | βcathodic (mVdec−1) | Jcorr (mAcm−2) | ηTafel | Rp (Ωcm2) | ηLPR | ||
0 | −732 | 0.03819 | 0.03836 | 6.215 × 10−6 | - | 1.22 × 103 | - | 0.072216 |
0.1 | −696 | 0.05404 | 0.14260 | 2.465 × 10−5 | 0 | 633.6 | 0 | 0.28638 |
0.2 | −701 | 0.06467 | 0.02803 | 2.298 × 10−5 | 0 | 724.9 | 0 | 0.26704 |
0.5 | −698 | 0.03672 | 0.10310 | 1.254 × 10−5 | 0 | 710.6 | 0 | 0.14569 |
0.8 | −700 | 0.04628 | 1.74730 | 2.334 × 10−5 | 0 | 749 | 0 | 0.27126 |
1.0 | −556 | 0.00655 | 0.00592 | 5.122 × 10−10 | 99.99 | 1.75 × 106 | 99.93 | 5.92 × 10−6 |
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Martins, G.R.; Guedes, D.; Marques de Paula, U.L.; de Oliveira, M.d.S.P.; Lutterbach, M.T.S.; Reznik, L.Y.; Sérvulo, E.F.C.; Alviano, C.S.; Ribeiro da Silva, A.J.; Alviano, D.S. Açaí (Euterpe oleracea Mart.) Seed Extracts from Different Varieties: A Source of Proanthocyanidins and Eco-Friendly Corrosion Inhibition Activity. Molecules 2021, 26, 3433. https://doi.org/10.3390/molecules26113433
Martins GR, Guedes D, Marques de Paula UL, de Oliveira MdSP, Lutterbach MTS, Reznik LY, Sérvulo EFC, Alviano CS, Ribeiro da Silva AJ, Alviano DS. Açaí (Euterpe oleracea Mart.) Seed Extracts from Different Varieties: A Source of Proanthocyanidins and Eco-Friendly Corrosion Inhibition Activity. Molecules. 2021; 26(11):3433. https://doi.org/10.3390/molecules26113433
Chicago/Turabian StyleMartins, Gabriel Rocha, Douglas Guedes, Urbano Luiz Marques de Paula, Maria do Socorro Padilha de Oliveira, Marcia Teresa Soares Lutterbach, Leila Yone Reznik, Eliana Flávia Camporese Sérvulo, Celuta Sales Alviano, Antonio Jorge Ribeiro da Silva, and Daniela Sales Alviano. 2021. "Açaí (Euterpe oleracea Mart.) Seed Extracts from Different Varieties: A Source of Proanthocyanidins and Eco-Friendly Corrosion Inhibition Activity" Molecules 26, no. 11: 3433. https://doi.org/10.3390/molecules26113433